US20040019981A1 - Direct dyeing composition for keratinous fibres comprising a cationic associative polyurethane - Google Patents

Direct dyeing composition for keratinous fibres comprising a cationic associative polyurethane Download PDF

Info

Publication number
US20040019981A1
US20040019981A1 US10/415,954 US41595403A US2004019981A1 US 20040019981 A1 US20040019981 A1 US 20040019981A1 US 41595403 A US41595403 A US 41595403A US 2004019981 A1 US2004019981 A1 US 2004019981A1
Authority
US
United States
Prior art keywords
composition
cationic
represent
group
direct
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US10/415,954
Other versions
US7108726B2 (en
Inventor
Francois Cottard
Roland de la Mettrie
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LOreal SA filed Critical LOreal SA
Assigned to L'OREAL S.A. reassignment L'OREAL S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COTTARD, FRANCOIS, DE LA METTRIE, ROLAND
Publication of US20040019981A1 publication Critical patent/US20040019981A1/en
Application granted granted Critical
Publication of US7108726B2 publication Critical patent/US7108726B2/en
Adjusted expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87Polyurethanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/10Preparations for permanently dyeing the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/542Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5426Polymers characterized by specific structures/properties characterized by the charge cationic

Definitions

  • the present invention relates to a composition for the direct dyeing of keratin fibers, in particular human keratin fibers and more particularly the hair, comprising at least one direct dye and at least one cationic associative polyurethane.
  • the Applicant has found that the thickening systems mentioned above do not make it possible to obtain intense and chromatic shades of low selectivity and good staying power, while at the same time leaving the treated hair in a good cosmetic condition. Moreover, the Applicant has also found that ready-to-use dye compositions containing the direct dye(s) and also the thickener systems of the prior art do not allow a sufficiently precise application without running or falls in viscosity over time.
  • One subject of the present invention is thus a direct dye composition for keratin fibers, in particular for human keratin fibers and more particularly the hair, comprising, in a medium that is suitable for dyeing, at least one direct dye, which is characterized in that it also comprises at least one cationic associative polyurethane.
  • Another subject of the invention relates to a ready-to-use composition for dyeing keratin fibers, which comprises at least one direct dye and at least one cationic associative polyurethane and an oxidizing agent.
  • ready-to-use composition means the composition intended to be applied in unmodified form to the keratin fibers, i.e. it may be stored in unmodified form before use, or may result from the extemporaneous mixing of two or more compositions.
  • the invention is also directed toward a process for the direct dyeing of keratin fibers, in particular for human keratin fibers and more particularly the hair, which consists in applying to the fibers a composition comprising, in a medium that is suitable for dyeing, at least one direct dye and at least one cationic associative polyurethane.
  • the invention is also directed toward a process for the lightening direct dyeing of keratin fibers, in particular for human keratin fibers and more particularly the hair, which consists in applying to the fibers an extemporaneous mixture of a composition A1 comprising, in a medium that is suitable for dyeing, at least one direct dye, and of a composition B1 comprising at least one oxidizing agent, composition A1 and/or composition B1 comprising at least one cationic associative polyurethane.
  • a subject of the invention is also devices for the direct dyeing and the lightening direct dyeing of human keratin fibers, and more particularly the hair, or two-compartment “kits”.
  • a two-compartment device for direct dyeing comprises a first compartment containing, in a medium that is suitable for dyeing, at least one direct dye, and a second compartment containing at least one cationic associative polyurethane.
  • compositions A1 comprising, in a medium that is suitable for dyeing, at least one direct dye
  • composition B1 comprising, in a medium that is suitable for dyeing, an oxidizing agent, at least one cationic associative polyurethane being present in composition A1 or composition B1, or in each of the compositions A1 and B1.
  • Associative polymers are polymers whose molecules are capable, in the formulation medium, of combining with each other or with the molecules of other compounds.
  • amphiphilic polymers i.e. polymers comprising one or more hydrophilic portions which make them water-soluble, and one or more hydrophobic zones (comprising at least one fatty chain) via which the polymers interact and assemble together or with other molecules.
  • the cationic associative polyurethanes according to the present invention are chosen more particularly from water-soluble or water-dispersible cationic associative amphiphilic polyurethanes.
  • water-soluble regarding the associative polyurethanes of the present invention means that these polymers have a solubility in water at room temperature of at least 1% by weight, i.e. up to this concentration, no precipitate is visible to the naked eye, and the solution is totally clear and uniform.
  • water-dispersible polyurethanes means polymers which, when suspended in water, spontaneously form globules that have a mean size, measured by light scattering on a Coulter machine, of between 5 nm and 600 nm and in particular between 5 nm and 500 nm.
  • R and R′ which may be identical or different, represent a hydrophobic group or a hydrogen atom
  • X and X′ which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively a group L′′;
  • L, L′ and L′′ which may be identical or different, represent a group derived from a diisocyanate
  • P and P′ which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group
  • Y represents a hydrophilic group
  • r is an integer between 1 and 100, preferably between 1 and 50 and in particular between 1 and 25,
  • n, m and p each range, independently of each other, from 0 to 1000;
  • the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group is the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
  • the only hydrophobic groups are the groups R and R′ at the chain ends.
  • R and R′ both independently represent a hydrophobic group
  • X and X′ each represent a group L′′
  • n and p are between 1 and 1000, and
  • L, L′, L′′, P, P′, Y and m have the meaning given above.
  • R and R′ both independently represent a hydrophobic group
  • X and X′ each represent a group L′′
  • n and p are 0, and L, L′, L′′, Y and m have the meaning given above.
  • n and p are 0 means that these polymers do not comprise units derived from a monomer containing an amine function, incorporated into the polymer during the polycondensation.
  • the protonated amine functions of these polyurethanes result from the hydrolysis of excess isocyanate functions, at the chain end, followed by alkylation of the primary amine functions formed with alkylating agents containing a hydrophobic group, i.e. compounds of the type RQ or R′Q, in which R and R′ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
  • R and R′ both independently represent a hydrophobic group
  • X and X′ both independently represent a group comprising a quaternary amine
  • n and p are zero, and
  • L, L′, Y and m have the meaning given above.
  • the number-average molecular mass of the cationic associative polyurethanes is preferably between 400 and 500 000, in particular between 1000 and 400 000 and ideally between 1000 and 300 000.
  • hydrophobic group means a radical or polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may contain one or more hetero atoms such as P, O, N or S, or a radical containing a perfluoro or silicone chain.
  • hydrophobic group denotes a hydrocarbon-based radical, it comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.
  • the hydrocarbon-based group is derived from a monofunctional compound.
  • the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer such as, for example, polybutadiene.
  • X and/or X′ denote(s) a group comprising a tertiary or quaternary amine
  • X and/or X′ may represent one of the following formulae:
  • R 2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a hetero atom chosen from N, S, O and P;
  • R 1 and R 3 which may be identical or different, denote a linear or branched C 1 -C 30 alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a hetero atom chosen from N, S, O and P;
  • a ⁇ is a physiologically acceptable counterion.
  • Z represents —O—, —S— or —NH—
  • R 4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a hetero atom chosen from N, S, O and P.
  • the groups P and P′ comprising an amine function may represent at least one of the following formulae:
  • R 5 and R 7 have the same meanings as R 2 defined above;
  • R 6 , R 8 and R 9 have the same meanings as R 1 and R 3 defined above;
  • R 10 represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more hetero atoms chosen from N, O, S and P;
  • a ⁇ is a physiologically acceptable counterion.
  • hydrophilic group means a polymeric or nonpolymeric water-soluble group.
  • hydrophilic polymer in accordance with one preferred embodiment, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides or a mixture of these polymers.
  • the hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or poly(propylene oxide).
  • the cationic associative polyurethanes of formula (Ia) according to the invention are formed from diisocyanates and from various compounds with functions containing a labile hydrogen.
  • the functions containing a labile hydrogen may be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas, respectively.
  • polyurethanes in the present invention encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.
  • a first type of compound involved in the preparation of the polyurethane of formula (Ia) is a compound comprising at least one unit containing an amine function.
  • This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to one preferential embodiment, this compound comprises two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol function.
  • a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low may also be used.
  • this compound may comprise more than one unit containing an amine function.
  • it is a polymer bearing a repetition of the unit containing an amine function.
  • Examples of compounds containing an amine function that may be mentioned include N-methyldiethanolamine, N-tert-butyldiethanolamine and N-sulfoethyldiethanolamine.
  • the second compound involved in the preparation of the polyurethane of formula (Ia) is a diisocyanate corresponding to the formula:
  • methylenediphenyl diisocyanate By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.
  • a third compound involved in the preparation of the polyurethane of formula (Ia) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (Ia).
  • This compound consists of a hydrophobic group and of a function containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
  • this compound may be a fatty alcohol such as, in particular, stearyl alcohol, dodecyl alcohol or decyl alcohol.
  • this compound may be, for example, [lacuna]-hydroxylated hydrogenated polybutadiene.
  • the hydrophobic group of the polyurethane of formula (Ia) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit.
  • the hydrophobic group is introduced via the quaternizing agent.
  • This quaternizing agent is a compound of the type RQ or R′Q, in which R and R′ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
  • the cationic associative polyurethane may also comprise a hydrophilic block.
  • This block is provided by a fourth type of compound involved in the preparation of the polymer.
  • This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low.
  • the functions containing a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing a labile hydrogen.
  • hydrophilic polymer When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers.
  • the hydrophilic compound is preferentially a polyether and especially a poly(ethylene oxide) or poly(propylene oxide).
  • the hydrophilic group termed Y in formula (Ia) is optional. Specifically, the units containing a quaternary amine or protonated function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution.
  • cationic associative polyurethanes comprising such a group are, however, preferred.
  • Said cationic associative polyurethanes are water-soluble or water-dispersible.
  • the cationic associative polyurethane(s) is (are) preferably used in an amount that may range from about 0.01% to 10% by weight relative to the total weight of the composition. More preferably, this amount ranges from about 0.1% to 5% by weight.
  • the direct dyes that may be used according to the invention are preferably chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo dyes, neutral, acidic or cationic quinone, and in particular anthraquinone, direct dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
  • azine dyes that may be mentioned are the following compounds:
  • indoamine dyes that may be used according to the invention, mention may be made of the following compounds:
  • the direct dye(s) preferably represent(s) from 0.001% to 20% by weight approximately relative to the total weight of the ready-to-use composition, and even more preferably from 0.005% to 10% by weight approximately.
  • compositions according to the invention may also comprise at least one amphoteric or cationic substantive polymer other than the cationic associative polyurethanes of the invention.
  • cationic polymer denotes any polymer containing cationic groups and/or groups that may be ionized into cationic groups.
  • the cationic polymers that may be used in accordance with the present invention may be chosen from all those already known per se as improving the cosmetic properties of the hair, i.e. especially those described in patent application EP-A-337 354 and in French patents FR-2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863.
  • the cationic polymers that are preferred are chosen from those containing units comprising primary, secondary, tertiary and/or quaternary amine groups, which may either form part of the main polymer chain or may be borne by a side substituent directly attached thereto.
  • the cationic polymers used generally have a number-average molecular mass of between 500 and 5 ⁇ 10 6 approximately and preferably between 10 3 and 3 ⁇ 10 6 approximately.
  • cationic polymers that may be mentioned more particularly are polymers of the polyamine, polyamino amide and polyquaternary ammonium type.
  • R 3 which may be identical or different, denote a hydrogen atom or a CH 3 radical
  • A which may be identical or different, represent a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;
  • R 4 , R 5 and R 6 which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group containing from 1 to 6 carbon atoms;
  • R 1 and R 2 which may be identical or different, represent hydrogen or an alkyl group containing from 1 to 6 carbon atoms, and preferably methyl or ethyl;
  • X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
  • the polymers of family (1) can also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C 1 -C 4 ) alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
  • comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C 1 -C 4 ) alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
  • copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide such as the product sold under the name Hercofloc by the company Hercules,
  • quaternized or nonquaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers such as the products sold under the name “Gafquat” by the company ISP, such as, for example, “Gafquat 734” or “Gafquat 755”, or alternatively the products known as “Copolymer 845, 958 and 937”. These polymers are described in detail in French patents 2 077 143 and 2 393 573,
  • dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers such as the product sold under the name Gaffix VC 713 by the company ISP,
  • quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name “Gafquat HS 100” by the company ISP.
  • Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
  • hydroxyalkylcelluloses for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
  • Such products are sold in particular under the trade names Jaguar C13 S, Jaguar C 15, Jaguar C 17 or Jaguar C162 by the company Meyhall.
  • polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such polymers are described in particular in French patent 1 583 363.
  • Polymers of this type are sold in particular under the name “Hercosett 57” by the company Hercules Inc. or alternatively under the name “PD 170” or “Delsette 101” by the company Hercules in the case of the adipic acid/epoxypropyl/diethylenetriamine copolymer.
  • R 9 denotes a hydrogen atom or a methyl radical
  • R 7 and R 8 independently of each other, denote an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower C 1 -C 4 amidoalkyl group, or R 7 and R 8 can denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidyl or morpholinyl
  • R 7 and R 8 independently of each other, preferably denote an alkyl group having from 1 to 4 carbon atoms
  • Y ⁇ is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
  • R 10 , R 11 , R 12 and R 13 which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or alternatively R 10 , R 11 , R 12 and R 13 , together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second hetero atom other than nitrogen, or alternatively R 10 , R 11 , R 12 and R 13 represent a linear or branched C 1 -C 6 alkyl radical substituted with a nitrile, ester, acyl or amide group or a group —CO—O—R 14 —D or —CO—NH—R 14 —D where R 14 is an alkylene and D is a quaternary ammonium group;
  • a 1 and B 1 represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
  • X ⁇ denotes an anion derived from a mineral or organic acid
  • a 1 , R 10 and R 12 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if A 1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B 1 can also denote a group —(CH 2 ) n —CO—D—OC—(CH 2 ) n — in which D denotes:
  • x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;
  • X ⁇ is an anion such as chloride or bromide.
  • These polymers generally have a number-average molecular mass of between 1000 and 100 000.
  • R 10 , R 11 , R 12 and R 13 which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 approximately, and X ⁇ is an anion derived from a mineral or organic acid.
  • D may be nothing or may represent a group —(CH 2 ) r —CO— in which r denotes a number equal to 4 or 7, X ⁇ is an anion.
  • Such polymers may be prepared according to the processes described in U.S. Pat. Nos. 4,157,388, 4,702,906 and 4,719,282. They are described in particular in patent application EP-A-122 324.
  • Quaternary polymers of vinylpyrrolidone and of vinylimidazole such as, for example, the products sold under the names Luviquat FC 905, FC 550 and FC 370 by the company BASF.
  • a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil can be used more particularly.
  • This dispersion is sold under the name “Salcare® SC 92” by the company Allied Colloids.
  • a crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester can also be used.
  • These dispersions are sold under the names “Salcare® SC 95” and “Salcare® SC 96” by the company Allied Colloids.
  • cationic polymers which can be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.
  • cationic polymers which may be used in the context of the present invention, it is preferred to use the polymers of families (1), (9), (10), (11) and (14) and even more preferably the polymers consisting of repeating units of formulae (W) and (U) below:
  • the concentration of cationic polymer in the composition according to the present invention may range from 0.01% to 10% by weight relative to the total weight of the composition, preferably from 0.05% to 5% and even more preferably from 0.1% to 3%.
  • K and M may also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups bears a carboxylic or sulfonic group linked via a hydrocarbon-based radical, or alternatively K and M form part of a chain of a polymer containing an ⁇ , ⁇ -dicarboxylic ethylene unit in which one of the carboxylic groups has been made to react with a polyamine comprising one or more primary or secondary amine groups.
  • amphoteric polymers corresponding to the above definition that are more particularly preferred are chosen from the following polymers:
  • a monomer derived from a vinyl compound bearing a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, ⁇ -chloroacrylic acid
  • a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamide and -acrylamide.
  • Such compounds are described in U.S. Pat. No. 3,836,
  • the vinyl compound may also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride.
  • the copolymers of acrylic acid and of the latter monomer are sold under the names Merquat 280, Merquat 295 and Merquat Plus 3330 by the company Calgon.
  • basic comonomer such as esters containing primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
  • N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.
  • the acidic comonomers are chosen more particularly from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid and alkyl monoesters, having 1 to 4 carbon atoms, of maleic or fumaric acids or anhydrides.
  • the preferred basic comonomers are aminoethyl, butylaminoethyl, N,N′-dimethylaminoethyl and N-tert-butylaminoethyl methacrylates.
  • copolymers whose CTFA (4th edition, 1991) name is Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer such as the products sold under the name Amphomer or Lovocryl 47 by the company National Starch are particularly used.
  • R 19 represents a divalent radical derived from a saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid containing an ethylenic double bond, an ester of a lower alkanol, having 1 to 6 carbon atoms, of these acids or a radical derived from the addition of any one of said acids to a bis(primary) or bis(secondary) amine, and Z denotes a bis(primary), mono- or bis(secondary) polyalkylene-polyamine radical and preferably represents:
  • this radical being derived from diethylenetriamine, from triethylenetetraamine or from dipropylenetriamine;
  • the saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid and acids containing an ethylenic double bond such as, for example, acrylic acid, methacrylic acid and itaconic acid.
  • the alkane sultones used in the alkylation are preferably propane sultone or butane sultone, and the salts of the alkylating agents are preferably the sodium or potassium salts.
  • R 20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group
  • y and z represent an integer from 1 to 3
  • R 21 and R 22 represent a hydrogen atom, methyl, ethyl or propyl
  • R 23 and R 24 represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R 23 and R 24 does not exceed 10.
  • the polymers comprising such units can also contain units derived from nonzwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.
  • R 25 represents a radical of formula:
  • R 26 , R 27 and R 28 which may be identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue which are optionally interrupted by one or more nitrogen atoms and/or optionally substituted with one or more amine, hydroxyl, carboxyl, alkylthio or sulfonic groups, an alkylthio residue in which the alkyl group bears an amino residue, at least one of the radicals R 26 , R 27 and R 28 being, in this case, a hydrogen atom;
  • R 26 , R 27 and R 28 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.
  • R 29 represents a hydrogen atom, a CH 3 O, CH 3 CH 2 O or phenyl radical
  • R 30 denotes hydrogen or a lower alkyl radical such as methyl or ethyl
  • R 31 denotes hydrogen or a lower alkyl radical such as methyl or ethyl
  • R 32 denotes a lower alkyl radical such as methyl or ethyl or a radical corresponding to the formula: —R 33 —N(R 31 ) 2
  • R 33 representing a —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 — or —CH 2 —CH(CH 3 )— group
  • R 31 having the meanings mentioned above
  • r is such that the molecular weight is between 500 and 6 000 000 and preferably between 1000 and 1 000 000.
  • X denotes the symbol E or E′, E or E′, which may be identical or different, denotes a divalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with hydroxyl groups and which can contain, in addition to the oxygen, nitrogen and sulfur atoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups;
  • E denotes the symbol E or E′ and at least once E′;
  • E having the meaning given above and E′ being a divalent radical which is an alkylene radical with a straight or branched chain having up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with one or more hydroxyl radicals and containing one or more nitrogen atoms, the nitrogen atom being substituted with an alkyl chain which is optionally interrupted by an oxygen atom and necessarily containing one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloroacetic acid or sodium chloroacetate.
  • (9) (C 1 -C 5 )alkyl vinyl ether/maleic anhydride copolymers partially modified by semiamidation with an N,N-dialkylaminoalkylamine such as N,N-dimethylaminopropylamine or by semiesterification with an N,N-dialkanolamine.
  • These copolymers can also contain other vinyl comonomers such as vinylcaprolactam.
  • amphoteric polymers that are particularly preferred according to the invention are those of family (1).
  • the amphoteric polymer(s) may represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight and even more preferably from 0.1% to 3% by weight relative to the total weight of the composition.
  • compositions of the invention preferably comprise one or more surfactants.
  • the surfactant(s) can be chosen without preference, alone or as mixtures, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.
  • surfactants that are suitable for carrying out the present invention are, in particular, the following:
  • anionic surfactants which can be used, alone or as mixtures, in the context of the present invention, mention may be made in particular (nonlimiting list) of salts (in particular alkaline salts, especially sodium salts, ammonium salts, amine salts, amino alcohol salts or magnesium salts) of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylarylpolyether sulfates, monoglyceride sulfates; alkyl sulfonates, alkyl phosphates, alkylamide sulfonates, alkylaryl sulfonates, ⁇ -olefin sulfonates, paraffin sulfonates; (C 6 -C 24 ) alkyl sulfosuccinates, (C 6 -C 24 ) alkyl ether sulfosuccinates, (C 6 -C 24 ) al
  • carboxylic esters of (C 6 -C 24 ) alkylpolyglycosides such as alkylglucoside citrates, alkylpolyglycoside tartrates and alkylpolyglycoside sulfosuccinates, alkylsulfosuccinamates; acyl isethionates and N-acyltaurates, the alkyl or acyl radical of all of these various compounds preferably containing from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group.
  • alkylpolyglycosides such as alkylglucoside citrates, alkylpolyglycoside tartrates and alkylpolyglycoside sulfosuccinates, alkylsulfosuccinamates; acyl isethionates and N-acyltaurates, the alkyl or acyl radical of all of these
  • anionic surfactants which can also be used, mention may also be made of fatty acid salts such as the salts of oleic, ricinoleic, palmitic and stearic acids, coconut oil acid or hydrogenated coconut oil acid; acyl lactylates in which the acyl radical contains 8 to 20 carbon atoms.
  • Alkyl-D-galactosideuronic acids and their salts polyoxyalkylenated (C 6 -C 24 ) alkyl ether carboxylic acids, polyoxyalkylenated (C 6 -C 24 ) alkylaryl ether carboxylic acids, polyoxyalkylenated (C 6 -C 24 ) alkylamido ether carboxylic acids and their salts, in particular those containing from 2 to 50 alkylene oxide, in particular ethylene oxide, groups, and mixtures thereof can also be used.
  • the nonionic surfactants are also compounds that are well known per se (see in particular in this respect “Handbook of Surfactants” by M. R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp. 116-178) and, in the context of the present invention, their nature is not a critical feature. Thus, they can be chosen in particular from (nonlimiting list) polyethoxylated or polypropoxylated alkylphenols, ⁇ -diols or alcohols having a fatty chain containing, for example, 8 to 18 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range in particular from 2 to 50.
  • copolymers of ethylene oxide and of propylene oxide, condensates of ethylene oxide and of propylene oxide with fatty alcohols polyethoxylated fatty amides preferably having from 2 to 30 mol of ethylene oxide, polyglycerolated fatty amides containing on average 1 to 5, and in particular 1.5 to 4, glycerol groups; polyethoxylated fatty amines preferably having from 2 to 30 mol of ethylene oxide; oxyethylenated fatty acid esters of sorbitan having from 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkylpolyglycosides, N-alkylglucamine derivatives, amine oxides such as (C 10 -C 14 )alkylamine oxides or N-acylaminopropylmorpholine oxides.
  • the alkylpolyglycosides constitute nonionic surfactants
  • amphoteric or zwitterionic surfactants can be, in particular (nonlimiting list), aliphatic secondary or tertiary amine derivatives in which the aliphatic radical is a linear or branched chain containing 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulfonate, sulfate, phosphate or phosphonate); mention may also be made of (C 8 -C 20 )alkylbetaines, sulfobetaines, (C 8 -C 20 )alkylamido(C 1 -C 6 )alkylbetaines or (C 8 -C 20 )alkylamido(C 1 -C 6 )alkylsulfobetaines.
  • aliphatic secondary or tertiary amine derivatives in which the aliphatic radical is a linear or branched chain containing 8 to 18 carbon atoms and containing at least one water-soluble ani
  • R 2 denotes an alkyl radical of an acid R 2 —COOH present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl radical, R 3 denotes a ⁇ -hydroxyethyl group and R 4 denotes a carboxymethyl group;
  • B represents —CH 2 CH 2 OX′
  • X′ denotes a —CH 2 CH 2 —COOH group or a hydrogen atom
  • Y′ denotes —COOH or a —CH 2 —CHOH—SO 3 H radical
  • R 2 ′ denotes an alkyl radical of an acid R 9 —COOH present in coconut oil or in hydrolyzed linseed oil, an alkyl radical, in particular a C 7 , C 9 , C 11 or C 13 alkyl radical, a C 17 alkyl radical and its iso form, an unsaturated C 17 radical.
  • cationic surfactants that may be mentioned in particular (nonlimiting list) are: primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated; quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium chlorides or bromides; imidazoline derivatives; or amine oxides of cationic nature.
  • the amounts of surfactants present in the composition according to the invention can range from 0.01% to 40% and preferably from 0.5% to 30% relative to the total weight of the composition.
  • compositions according to the invention can also contain other agents for adjusting the rheology, such as cellulose-based thickeners (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, etc.), guar gum and its derivatives (hydroxypropyl guar, etc.), gums of microbial origin (xanthan gum, scleroglucan gum, etc.), synthetic thickeners such as crosslinked acrylic acid or acrylamidopropanesulfonic acid homopolymers and ionic or nonionic associative polymers such as the polymers sold under the names Pemulen TR1 or TR2 by the company Goodrich, Salcare SC90 by the company Allied Colloids, Aculyn 22, 28, 33, 44 or 46 by the company Rohm & Haas, and Elfacos T210 and T212 by the company Akzo.
  • cellulose-based thickeners hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, etc.
  • guar gum and its derivatives hydroxy
  • These additional thickeners can represent from 0.01% to 10% by weight relative to the total weight of the composition.
  • the medium of the composition that is suitable for dyeing is preferably an aqueous medium consisting of water and may advantageously contain cosmetically acceptable organic solvents including, more particularly, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, or glycols or glycol ethers such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol and diethylene glycol alkyl ethers such as, for example, diethylene glycol monoethyl ether or monobutyl ether.
  • the solvents may then be present in concentrations of between about 0.5% and 20% and preferably between about 2% and 10% by weight relative to the total weight of the composition.
  • Composition A may also comprise an effective amount of other agents, which are previously known elsewhere for direct dyeing, such as various common adjuvants, for instance sequestering agents such as EDTA and etidronic acid, UV screening agents, waxes, volatile or nonvolatile, cyclic or linear or branched silicones, which are possibly organomodified (especially with amine groups), preserving agents, ceramides, pseudoceramides, plant, mineral or synthetic oils, vitamins or provitamins, for instance panthenol, opacifiers, associative polymers other than those of the invention, and in particular nonionic associative polyurethane polyethers.
  • agents which are previously known elsewhere for direct dyeing, such as various common adjuvants, for instance sequestering agents such as EDTA and etidronic acid, UV screening agents, waxes, volatile or nonvolatile, cyclic or linear or branched silicones, which are possibly organomodified (especially with amine groups), preserving agents,
  • the oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, and persalts such as perborates and persulfates. It is particularly preferred to use hydrogen peroxide.
  • This oxidizing agent advantageously consists of an aqueous hydrogen peroxide solution whose titer may range, more particularly, from about 1 to 40 volumes and even more preferably from about 5 to 40 volumes.
  • Oxidizing agents that may also be used are one or more redox enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase), where appropriate in the presence of their respective donor or cofactor.
  • redox enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase)
  • the pH of the ready-to-use composition is generally between the values 2 and 12. It is preferably between 3 and 11, and may be adjusted to the desired value by means of acidifying or basifying agents that are well known in the prior art in the dyeing of keratin fibers.
  • the pH of the ready-to-use mixture is greater than 7 and even more preferentially greater than 8.
  • basifying agents are aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine and also derivatives thereof, oxyethylenated and/or oxypropylenated hydroxyalkylamines and ethylenediamines, sodium hydroxide, potassium hydroxide and the compounds of formula (XIX) below:
  • R is a propylene residue optionally substituted with a hydroxyl group or a C 1 -C 4 alkyl radical
  • R 38 , R 39 , R 40 and R 41 which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical or a C 1 -C 4 hydroxyalkyl radical.
  • the acidifying agents are conventionally, for example, mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, carboxylic acids, for instance tartaric acid, citric acid or lactic acid, or sulfonic acids.
  • the dyeing process according to the invention preferably consists in applying the oxidant-free ready-to-use composition A or the composition prepared extemporaneously at the time of use from compositions A1 and B1 described above, to wet or dry keratin fibers, and leaving the composition to act for an action time preferably ranging from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, rinsing the fibers and then optionally washing them with shampoo, followed by rinsing them again and drying them.
  • composition A′ comprising at least one direct dye but without cationic associative polyurethane
  • composition A′′ comprising at least one cationic associative polyurethane polymer
  • Oxidizing composition Fatty alcohol 2.3 Oxyethylenated fatty alcohol 0.6 Fatty amide 0.9 Glycerol 0.5 Hydrogen peroxide 7.5 Fragrance qs Demineralized water qs 100
  • Dye composition A B Oxyethylenated fatty alcohols 32.5 32.5 Oleic acid 2 2 Oleyl alcohol 1.8 1.8 Fatty amide 4 4 Glycerol 3 3 Cationic polymer of formula (W) as a 1.2 AM* 1.2 AM* 60% solution in water Merquat 280 2 2 Sequestering agent Qs qs Reducing agent Qs qs Aqueous ammonia (20% NH 3 ) 8 8 Diamino-1,4-nitro-2- 0.6 0.6 benzene Polymer 1 0.3 AM* Polymer 2 0.3 AM* Water qs 100 g 100 g
  • Polymer 1 is the following polymer:
  • R 4 methylenedicyclohexyl
  • Polymer 2 is the following polymer:
  • R 4 methylenedicyclohexyl
  • the dye compositions were mixed, at the time of use, in a plastic bowl for 2 minutes, with the oxidizing composition given above, in a proportion of 1 part of dye composition per 1.5 parts of oxidizing composition.
  • This composition was applied for 30 minutes to gray hair containing 90% white hairs. After rinsing and drying, the hair was dyed a strong red.

Abstract

The invention concerns a direct dyeing composition for keratinous fibres, in particular for human keratinous fibres and more particularly hair, comprising, in a medium suitable for dyeing, at least a direct colouring agent, and furthermore at least a cationic associative polyurethane. The invention also concerns dyeing methods and devices using said composition.

Description

  • The present invention relates to a composition for the direct dyeing of keratin fibers, in particular human keratin fibers and more particularly the hair, comprising at least one direct dye and at least one cationic associative polyurethane. [0001]
  • It is known practice to dye keratin fibers, and in particular human hair, with dye compositions containing direct dyes, in particular nitrobenzene dyes, acidic azo dyes, cationic azo dyes, anthraquinone dyes and natural dyes. These colorations may be produced by directly applying to the keratin fibers the composition containing the direct dye(s) or by applying a mixture, prepared extemporaneously, of a composition containing the direct dye(s) with a composition containing an oxidizing bleaching agent, which is preferably aqueous hydrogen peroxide solution. The coloration is then referred to as lightening direct dyeing. [0002]
  • To localize the dye product on application to the hair so that it does not run down the face or beyond the areas which it is proposed to dye, use has been made hitherto of conventional thickeners such as crosslinked polyacrylic acid, hydroxyethylcelluloses, waxes or mixtures of nonionic surfactants with an HLB (Hydrophilic-Lipophilic Balance) value, which, when suitably chosen, give rise to a gelling effect when they are diluted with water and/or surfactants. [0003]
  • However, the Applicant has found that the thickening systems mentioned above do not make it possible to obtain intense and chromatic shades of low selectivity and good staying power, while at the same time leaving the treated hair in a good cosmetic condition. Moreover, the Applicant has also found that ready-to-use dye compositions containing the direct dye(s) and also the thickener systems of the prior art do not allow a sufficiently precise application without running or falls in viscosity over time. [0004]
  • After considerable research conducted in this matter, the Applicant has now discovered that it is possible to obtain direct dye compositions that do not run and thus remain satisfactorily localized at the point of application, and that also make it possible to obtain powerful and chromatic (luminous) shades with low selectivity and good staying power with respect to chemical agents (shampoos, permanent-waving agents, etc.) or natural agents (light, perspiration, etc.) while at the same time giving the hair good cosmetic properties, if an effective amount of a cationic associative polyurethane is introduced either (i) into the composition containing at least one direct dye [or composition A1], or (ii) into the oxidizing composition [or composition B1] used for lightening direct dyeing, or (iii) into both compositions at the same time. [0005]
  • These discoveries form the basis of the present invention. [0006]
  • One subject of the present invention is thus a direct dye composition for keratin fibers, in particular for human keratin fibers and more particularly the hair, comprising, in a medium that is suitable for dyeing, at least one direct dye, which is characterized in that it also comprises at least one cationic associative polyurethane. [0007]
  • Another subject of the invention relates to a ready-to-use composition for dyeing keratin fibers, which comprises at least one direct dye and at least one cationic associative polyurethane and an oxidizing agent. [0008]
  • For the purposes of the invention, the expression “ready-to-use composition” means the composition intended to be applied in unmodified form to the keratin fibers, i.e. it may be stored in unmodified form before use, or may result from the extemporaneous mixing of two or more compositions. [0009]
  • The invention is also directed toward a process for the direct dyeing of keratin fibers, in particular for human keratin fibers and more particularly the hair, which consists in applying to the fibers a composition comprising, in a medium that is suitable for dyeing, at least one direct dye and at least one cationic associative polyurethane. The invention is also directed toward a process for the lightening direct dyeing of keratin fibers, in particular for human keratin fibers and more particularly the hair, which consists in applying to the fibers an extemporaneous mixture of a composition A1 comprising, in a medium that is suitable for dyeing, at least one direct dye, and of a composition B1 comprising at least one oxidizing agent, composition A1 and/or composition B1 comprising at least one cationic associative polyurethane. [0010]
  • A subject of the invention is also devices for the direct dyeing and the lightening direct dyeing of human keratin fibers, and more particularly the hair, or two-compartment “kits”. [0011]
  • A two-compartment device for direct dyeing according to the invention comprises a first compartment containing, in a medium that is suitable for dyeing, at least one direct dye, and a second compartment containing at least one cationic associative polyurethane. [0012]
  • Other two-compartment devices for lightening direct dyeing according to the invention comprise a compartment that contains a composition A1 comprising, in a medium that is suitable for dyeing, at least one direct dye, and another compartment contains a composition B1 comprising, in a medium that is suitable for dyeing, an oxidizing agent, at least one cationic associative polyurethane being present in composition A1 or composition B1, or in each of the compositions A1 and B1. [0013]
  • However, other characteristics, aspects, subjects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow. [0014]
  • Associative polymers are polymers whose molecules are capable, in the formulation medium, of combining with each other or with the molecules of other compounds. [0015]
  • One special case of associative polymers is amphiphilic polymers, i.e. polymers comprising one or more hydrophilic portions which make them water-soluble, and one or more hydrophobic zones (comprising at least one fatty chain) via which the polymers interact and assemble together or with other molecules. [0016]
  • Cationic Associative Polyurethanes
  • The cationic associative polyurethanes according to the present invention are chosen more particularly from water-soluble or water-dispersible cationic associative amphiphilic polyurethanes. [0017]
  • The term “water-soluble” regarding the associative polyurethanes of the present invention means that these polymers have a solubility in water at room temperature of at least 1% by weight, i.e. up to this concentration, no precipitate is visible to the naked eye, and the solution is totally clear and uniform. [0018]
  • The term “water-dispersible” polyurethanes means polymers which, when suspended in water, spontaneously form globules that have a mean size, measured by light scattering on a Coulter machine, of between 5 nm and 600 nm and in particular between 5 nm and 500 nm. [0019]
  • The family of cationic associative polyurethanes according to the invention was described by the Applicant in French patent application No 00/09609; it may be represented by the general formula (Ia) below: [0020]
  • R—X—(P)n—[L—(Y)m]r—L′—(P′)p—X′—R′  (Ia)
  • in which: [0021]
  • R and R′, which may be identical or different, represent a hydrophobic group or a hydrogen atom; [0022]
  • X and X′, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively a group L″; [0023]
  • L, L′ and L″, which may be identical or different, represent a group derived from a diisocyanate; [0024]
  • P and P′, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group; [0025]
  • Y represents a hydrophilic group; [0026]
  • r is an integer between 1 and 100, preferably between 1 and 50 and in particular between 1 and 25, [0027]
  • n, m and p each range, independently of each other, from 0 to 1000; [0028]
  • the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group. [0029]
  • In one preferred embodiment of the polyurethanes of the present invention, the only hydrophobic groups are the groups R and R′ at the chain ends. [0030]
  • One preferred family of cationic associative polyurethanes is the one corresponding to formula (Ia) described above and in which: [0031]
  • R and R′ both independently represent a hydrophobic group, [0032]
  • X and X′ each represent a group L″, [0033]
  • n and p are between 1 and 1000, and [0034]
  • L, L′, L″, P, P′, Y and m have the meaning given above. [0035]
  • Another preferred family of cationic associative polyurethanes is the one corresponding to formula (Ia) above in which: [0036]
  • R and R′ both independently represent a hydrophobic group, X and X′ each represent a group L″, n and p are 0, and L, L′, L″, Y and m have the meaning given above. [0037]
  • The fact that n and p are 0 means that these polymers do not comprise units derived from a monomer containing an amine function, incorporated into the polymer during the polycondensation. The protonated amine functions of these polyurethanes result from the hydrolysis of excess isocyanate functions, at the chain end, followed by alkylation of the primary amine functions formed with alkylating agents containing a hydrophobic group, i.e. compounds of the type RQ or R′Q, in which R and R′ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc. [0038]
  • Yet another preferred family of cationic associative polyurethanes is the one corresponding to formula (Ia) above in which: [0039]
  • R and R′ both independently represent a hydrophobic group, [0040]
  • X and X′ both independently represent a group comprising a quaternary amine, [0041]
  • n and p are zero, and [0042]
  • L, L′, Y and m have the meaning given above. [0043]
  • The number-average molecular mass of the cationic associative polyurethanes is preferably between 400 and 500 000, in particular between 1000 and 400 000 and ideally between 1000 and 300 000. [0044]
  • The expression “hydrophobic group” means a radical or polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may contain one or more hetero atoms such as P, O, N or S, or a radical containing a perfluoro or silicone chain. When the hydrophobic group denotes a hydrocarbon-based radical, it comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms. [0045]
  • Preferentially, the hydrocarbon-based group is derived from a monofunctional compound. [0046]
  • By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer such as, for example, polybutadiene. [0047]
  • When X and/or X′ denote(s) a group comprising a tertiary or quaternary amine, X and/or X′ may represent one of the following formulae: [0048]
    Figure US20040019981A1-20040205-C00001
  • in which: [0049]
  • R[0050] 2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a hetero atom chosen from N, S, O and P;
  • R[0051] 1 and R3, which may be identical or different, denote a linear or branched C1-C30 alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a hetero atom chosen from N, S, O and P;
  • A[0052] is a physiologically acceptable counterion.
  • The groups L, L′ and L″ represent a group of formula: [0053]
    Figure US20040019981A1-20040205-C00002
  • in which: [0054]
  • Z represents —O—, —S— or —NH—; and [0055]
  • R[0056] 4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a hetero atom chosen from N, S, O and P.
  • The groups P and P′ comprising an amine function may represent at least one of the following formulae: [0057]
    Figure US20040019981A1-20040205-C00003
  • in which: [0058]
  • R[0059] 5 and R7 have the same meanings as R2 defined above;
  • R[0060] 6, R8 and R9 have the same meanings as R1 and R3 defined above;
  • R[0061] 10 represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more hetero atoms chosen from N, O, S and P; and
  • A[0062] is a physiologically acceptable counterion.
  • As regards the meaning of Y, the term “hydrophilic group” means a polymeric or nonpolymeric water-soluble group. [0063]
  • By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol. [0064]
  • When it is a hydrophilic polymer, in accordance with one preferred embodiment, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or poly(propylene oxide). [0065]
  • The cationic associative polyurethanes of formula (Ia) according to the invention are formed from diisocyanates and from various compounds with functions containing a labile hydrogen. The functions containing a labile hydrogen may be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas, respectively. The term “polyurethanes” in the present invention encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof. [0066]
  • A first type of compound involved in the preparation of the polyurethane of formula (Ia) is a compound comprising at least one unit containing an amine function. This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to one preferential embodiment, this compound comprises two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol function. A mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low may also be used. [0067]
  • As mentioned above, this compound may comprise more than one unit containing an amine function. In this case, it is a polymer bearing a repetition of the unit containing an amine function. [0068]
  • Compounds of this type may be represented by one of the following formulae: [0069]
  • HZ—(P)n—ZH
  • or [0070]
  • HZ—(P′)p—ZH
  • in which Z, P, P′, n and p are as defined above. [0071]
  • Examples of compounds containing an amine function that may be mentioned include N-methyldiethanolamine, N-tert-butyldiethanolamine and N-sulfoethyldiethanolamine. [0072]
  • The second compound involved in the preparation of the polyurethane of formula (Ia) is a diisocyanate corresponding to the formula: [0073]
  • O═C═N—R4—N═C═O
  • in which R[0074] 4 is as defined above.
  • By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate. [0075]
  • A third compound involved in the preparation of the polyurethane of formula (Ia) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (Ia). [0076]
  • This compound consists of a hydrophobic group and of a function containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function. [0077]
  • By way of example, this compound may be a fatty alcohol such as, in particular, stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound comprises a polymeric chain, it may be, for example, [lacuna]-hydroxylated hydrogenated polybutadiene. [0078]
  • The hydrophobic group of the polyurethane of formula (Ia) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit. Thus, the hydrophobic group is introduced via the quaternizing agent. This quaternizing agent is a compound of the type RQ or R′Q, in which R and R′ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc. [0079]
  • The cationic associative polyurethane may also comprise a hydrophilic block. This block is provided by a fourth type of compound involved in the preparation of the polymer. This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low. [0080]
  • The functions containing a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing a labile hydrogen. [0081]
  • By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol. [0082]
  • When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and especially a poly(ethylene oxide) or poly(propylene oxide). [0083]
  • The hydrophilic group termed Y in formula (Ia) is optional. Specifically, the units containing a quaternary amine or protonated function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution. [0084]
  • Although the presence of a hydrophilic group Y is optional, cationic associative polyurethanes comprising such a group are, however, preferred. [0085]
  • Said cationic associative polyurethanes are water-soluble or water-dispersible. [0086]
  • In the dye composition according to the invention, the cationic associative polyurethane(s) is (are) preferably used in an amount that may range from about 0.01% to 10% by weight relative to the total weight of the composition. More preferably, this amount ranges from about 0.1% to 5% by weight. [0087]
  • The direct dyes that may be used according to the invention are preferably chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo dyes, neutral, acidic or cationic quinone, and in particular anthraquinone, direct dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes. [0088]
  • Among the benzene-based direct dyes that may be used according to the invention, mention may be made, in a nonlimiting manner, of the following compounds: [0089]
  • 1,2-damino-2-nitrobenzene [0090]
  • 1-amino-2-nitro-4-β-hydroxyethylaminobenzene [0091]
  • 1-amino-2-nitro-4-bis(β-hydroxyethyl)aminobenzene [0092]
  • 1,4-bis(β-hydroxyethylamino)-2-nitrobenzene [0093]
  • 1-β-hydroxyethylamino-2-nitro-4-bis(β-hydroxyethylamino)benzene [0094]
  • 1-β-hydroxyethylamino-2-nitro-4-aminobenzene [0095]
  • 1-β-hydroxyethylamino-2-nitro-4-(ethyl)(β-hydroxyethyl)aminobenzene [0096]
  • 1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene [0097]
  • 1-amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene [0098]
  • 1,2-diamino-4-nitrobenzene [0099]
  • 1-amino-2-β-hydroxyethylamino-5-nitrobenzene [0100]
  • 1,2-bis(β-hydroxyethylamino)-4-nitrobenzene [0101]
  • 1-amino-2-tris(hydroxymethyl)methylamino-5-nitrobenzene [0102]
  • 1-hydroxy-2-amino-5-nitrobenzene [0103]
  • 1-hydroxy-2-amino-4-nitrobenzene [0104]
  • 1-hydroxy-3-nitro-4-aminobenzene [0105]
  • 1-hydroxy-2-amino-4,6-dinitrobenzene [0106]
  • 1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene [0107]
  • 1-methoxy-2-β-hydroxyethylamino-5-nitrobenzene [0108]
  • 1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene [0109]
  • 1-β,γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene [0110]
  • 1-β-hydroxyethylamino-4-β,γ-dihydroxypropyloxy-2-nitrobenzene [0111]
  • 1-β,γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene [0112]
  • 1-β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene [0113]
  • 1-β-hydroxyethylamino-3-methyl-2-nitrobenzene [0114]
  • 1-β-aminoethylamino-5-methoxy-2-nitrobenzene [0115]
  • 1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene [0116]
  • 1-hydroxy-2-chloro-6-amino-4-nitrobenzene [0117]
  • 1-hydroxy-6-bis(β-hydroxyethyl)amino-3-nitrobenzene [0118]
  • 1-β-hydroxyethylamino-2-nitrobenzene [0119]
  • 1-hydroxy-4-β-hydroxyethylamino-3-nitrobenzene. [0120]
  • Among the azo direct dyes that may be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714 954, the content of which forms an integral part of the invention. [0121]
  • Among the azo direct dyes, mention may also be made of the following dyes, described in the Color Index International 3rd edition: [0122]
  • Disperse Red 17 [0123]
  • Acid Yellow 9 [0124]
  • Acid Black 1 [0125]
  • Basic Red 22 [0126]
  • Basic Red 76 [0127]
  • Basic Yellow 57 [0128]
  • Basic Brown 16 [0129]
  • Acid Yellow 36 [0130]
  • Acid Orange 7 [0131]
  • Acid Red 33 [0132]
  • Acid Red 35 [0133]
  • Basic Brown 17 [0134]
  • Acid Yellow 23 [0135]
  • Acid Orange 24 [0136]
  • Disperse Black 9. [0137]
  • Mention may also be made of 1-(4′-aminodiphenylazo)-2-methyl-4-bis(β-hydroxyethyl)aminobenzene and 4-hydroxy-3-(2-methoxyphenylazo)-1-naphthalenesulfonic acid. [0138]
  • Among the quinone direct dyes that may be mentioned are the following dyes: [0139]
  • Disperse Red 15 [0140]
  • Solvent Violet 13 [0141]
  • Acid Violet 43 [0142]
  • Disperse Violet 1 [0143]
  • Disperse Violet 4 [0144]
  • Disperse Blue 1 [0145]
  • Disperse Violet 8 [0146]
  • Disperse Blue 3 [0147]
  • Disperse Red 11 [0148]
  • Acid Blue 62 [0149]
  • Disperse Blue 7 [0150]
  • Basic Blue 22 [0151]
  • Disperse Violet 15 [0152]
  • Basic Blue 99 [0153]
  • also the following compounds: [0154]
  • 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone [0155]
  • 1-aminopropylamino-4-methylaminoanthraquinone [0156]
  • 1-aminopropylaminoanthraquinone [0157]
  • 5-β-hydroxyethyl-1,4-diaminoanthraquinone [0158]
  • 2-aminoethylaminoanthraquinone [0159]
  • 1,4-bis(β,γ-dihydroxypropylamino)anthraquinone. [0160]
  • Among the azine dyes that may be mentioned are the following compounds: [0161]
  • Basic Blue 17 [0162]
  • Basic Red 2. [0163]
  • Among the triarylmethane dyes that may be used according to the invention, mention may be made of the following compounds: [0164]
  • Basic Green 1 [0165]
  • Acid Blue 9 [0166]
  • Basic Violet 3 [0167]
  • Basic Violet 14 [0168]
  • Basic Blue 7 [0169]
  • Acid Violet 49 [0170]
  • Basic Blue 26 [0171]
  • Acid Blue 7 [0172]
  • Among the indoamine dyes that may be used according to the invention, mention may be made of the following compounds: [0173]
  • 2-β-hydroxyethylamino-5-[bis(β-4′-hydroxyethyl)amino]anilino-1,4-benzoquinone [0174]
  • 2-β-hydroxyethylamino-5-(2′-methoxy-4′-amino)anilino-1,4-benzoquinone [0175]
  • 3-N-(2′-chloro-4′-hydroxy)phenylacetylamino-6-methoxy-1,4-benzoquinoneimine [0176]
  • 3-N-(3′-chloro-4′-methylamino)phenylureido-6-methyl-1,4-benzoquinoneimine [0177]
  • 3-[4′-N-(ethyl,carbamylmethyl)amino]phenylureido-6-methyl-1,4-benzoquinoneimine [0178]
  • Among the natural direct dyes that may be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosoin and apigenidin. Extracts or decoctions containing these natural dyes, and especially henna-based poultices or extracts, may also be used. [0179]
  • The direct dye(s) preferably represent(s) from 0.001% to 20% by weight approximately relative to the total weight of the ready-to-use composition, and even more preferably from 0.005% to 10% by weight approximately. [0180]
  • More particularly, the compositions according to the invention may also comprise at least one amphoteric or cationic substantive polymer other than the cationic associative polyurethanes of the invention. [0181]
  • Cationic Polymers
  • For the purposes of the present invention, the term “cationic polymer” denotes any polymer containing cationic groups and/or groups that may be ionized into cationic groups. [0182]
  • The cationic polymers that may be used in accordance with the present invention may be chosen from all those already known per se as improving the cosmetic properties of the hair, i.e. especially those described in patent application EP-A-337 354 and in French patents FR-2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863. [0183]
  • The cationic polymers that are preferred are chosen from those containing units comprising primary, secondary, tertiary and/or quaternary amine groups, which may either form part of the main polymer chain or may be borne by a side substituent directly attached thereto. [0184]
  • The cationic polymers used generally have a number-average molecular mass of between 500 and 5×10[0185] 6 approximately and preferably between 103 and 3×106 approximately.
  • Among the cationic polymers that may be mentioned more particularly are polymers of the polyamine, polyamino amide and polyquaternary ammonium type. [0186]
  • These are known products. They are described in particular in French patents Nos 2 505 348 and 2 542 997. Among said polymers, mention may be made of: [0187]
  • (1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formula (I), (II), (III) or (IV) below: [0188]
    Figure US20040019981A1-20040205-C00004
  • in which: [0189]
  • R[0190] 3, which may be identical or different, denote a hydrogen atom or a CH3 radical;
  • A, which may be identical or different, represent a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms; [0191]
  • R[0192] 4, R5 and R6, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group containing from 1 to 6 carbon atoms;
  • R[0193] 1 and R2, which may be identical or different, represent hydrogen or an alkyl group containing from 1 to 6 carbon atoms, and preferably methyl or ethyl; X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
  • The polymers of family (1) can also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C[0194] 1-C4) alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
  • Thus, among these polymers of family (1), mention may be made of: [0195]
  • copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name Hercofloc by the company Hercules, [0196]
  • the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described, for example, in patent application EP-A-080 976 and sold under the name Bina Quat P 100 by the company Ciba Geigy, [0197]
  • the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate sold under the name Reten by the company Hercules, [0198]
  • quaternized or nonquaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name “Gafquat” by the company ISP, such as, for example, “Gafquat 734” or “Gafquat 755”, or alternatively the products known as “Copolymer 845, 958 and 937”. These polymers are described in detail in French patents 2 077 143 and 2 393 573, [0199]
  • dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP, [0200]
  • vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers sold in particular under the name Styleze CC 10 by ISP, and [0201]
  • quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers, such as the product sold under the name “Gafquat HS 100” by the company ISP. [0202]
  • (2) The cellulose ether derivatives containing quaternary ammonium groups, described in French patent 1 492 597, and in particular polymers sold under the names “JR” (JR 400, JR 125 and JR 30M) or “LR” (LR 400 or LR 30M) by the company Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group. [0203]
  • (3) Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. [0204]
  • The commercial products corresponding to this definition are more particularly the products sold under the names “Celquat L 200” and “Celquat H 100” by the company National Starch. [0205]
  • (4) The cationic polysaccharides described more particularly in U.S. Pat. Nos. 3,589,578 and 4,031,307, such as guar gums containing cationic trialkylammonium groups. Guar gums modified with a salt (e.g. chloride) of 2,3-epoxypropyltrimethylammonium are used, for example. [0206]
  • Such products are sold in particular under the trade names Jaguar C13 S, Jaguar C 15, Jaguar C 17 or Jaguar C162 by the company Meyhall. [0207]
  • (5) Polymers consisting of piperazinyl units and of divalent alkylene or hydroxyalkylene radicals containing straight or branched chains, optionally interrupted by oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings, as well as the oxidation and/or quaternization products of these polymers. Such polymers are described, in particular, in French patents 2 162 025 and 2 280 361. [0208]
  • (6) Water-soluble polyamino amides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyamino amides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyamino amide; these polyamino amides can be alkylated or, if they contain one or more tertiary amine functions, they can be quaternized. Such polymers are described, in particular, in French patents 2 252 840 and 2 368 508. [0209]
  • (7) The polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such polymers are described in particular in French patent 1 583 363. [0210]
  • Among these derivatives, mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name “Cartaretine F, F4 or F8” by the company Sandoz. [0211]
  • (8) The polymers obtained by reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid is between 0.8:1 and 1.4:1; the polyamino amide resulting therefrom is reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyamino amide of between 0.5:1 and 1.8:1. Such polymers are described in particular in U.S. Pat. Nos. 3,227,615 and 2,961,347. [0212]
  • Polymers of this type are sold in particular under the name “Hercosett 57” by the company Hercules Inc. or alternatively under the name “PD 170” or “Delsette 101” by the company Hercules in the case of the adipic acid/epoxypropyl/diethylenetriamine copolymer. [0213]
  • (9) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers containing, as main constituent of the chain, units corresponding to formula (V) or (VI): [0214]
    Figure US20040019981A1-20040205-C00005
  • in which formulae k and t are equal to 0 or 1, the sum k+t being equal to 1; R[0215] 9 denotes a hydrogen atom or a methyl radical; R7 and R8, independently of each other, denote an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower C1-C4 amidoalkyl group, or R7 and R8 can denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidyl or morpholinyl; R7 and R8, independently of each other, preferably denote an alkyl group having from 1 to 4 carbon atoms; Yis an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. These polymers are described in particular in French patent 2 080 759 and in its Certificate of Addition 2 190 406.
  • Among the polymers defined above, mention may be made more particularly of the dimethyldiallylammonium chloride homopolymer sold under the name “Merquat 100” by the company Calgon (and its homologs of low weight-average molecular mass) and the copolymers of diallyldimethylammonium chloride and of acrylamide, sold under the name “Merquat 550”. [0216]
  • (10) The quaternary diammonium polymer containing repeating units corresponding to the formula: [0217]
    Figure US20040019981A1-20040205-C00006
  • in which formula (VII): [0218]
  • R[0219] 10, R11, R12 and R13, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or alternatively R10, R11, R12 and R13, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second hetero atom other than nitrogen, or alternatively R10, R11, R12 and R13 represent a linear or branched C1-C6 alkyl radical substituted with a nitrile, ester, acyl or amide group or a group —CO—O—R14—D or —CO—NH—R14—D where R14 is an alkylene and D is a quaternary ammonium group;
  • A[0220] 1 and B1 represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
  • X[0221] denotes an anion derived from a mineral or organic acid;
  • A[0222] 1, R10 and R12 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 can also denote a group —(CH2)n—CO—D—OC—(CH2)n— in which D denotes:
  • a) a glycol residue of formula: —O—Z—O—, where Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae: [0223]
  • —(CH2—CH2—O)x—CH2—CH2
  • —[CH2—CH(CH3)—O]y—CH2—CH(CH3)—
  • where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; [0224]  
  • b) a bis-secondary diamine residue such as a piperazine derivative; [0225]
  • c) a bis-primary diamine residue of formula: —NH—Y—NH—, where Y denotes a linear or branched hydrocarbon-based radical, or alternatively the divalent radical [0226]
  • —CH2—CH2—S—S—CH2—CH2—;
  • d) a ureylene group of formula: —NH—CO—NH—. [0227]
  • Preferably, X[0228] is an anion such as chloride or bromide.
  • These polymers generally have a number-average molecular mass of between 1000 and 100 000. [0229]
  • Polymers of this type are described in particular in French patents 2 320 330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 and U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020. [0230]
  • It is more particularly possible to use polymers that consist of repeating units corresponding to formula (VIII) below: [0231]
    Figure US20040019981A1-20040205-C00007
  • in which R[0232] 10, R11, R12 and R13, which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 approximately, and Xis an anion derived from a mineral or organic acid.
  • (11) Polyquaternary ammonium polymers consisting of repeating units of formula (IX): [0233]
    Figure US20040019981A1-20040205-C00008
  • in which p denotes an integer ranging from 1 to 6 approximately, D may be nothing or may represent a group —(CH[0234] 2)r—CO— in which r denotes a number equal to 4 or 7, Xis an anion.
  • Such polymers may be prepared according to the processes described in U.S. Pat. Nos. 4,157,388, 4,702,906 and 4,719,282. They are described in particular in patent application EP-A-122 324. [0235]
  • Among these products, mention may be made, for example, of “Mirapol A 15”, “Mirapol AD1”, “Mirapol AZ1” and “Mirapol 175” sold by the company Miranol. [0236]
  • (12) Quaternary polymers of vinylpyrrolidone and of vinylimidazole, such as, for example, the products sold under the names Luviquat FC 905, FC 550 and FC 370 by the company BASF. [0237]
  • (13) Polyamines such as Polyquart H sold by Henkel, which is given under the reference name “Polyethylene glycol (15) tallow polyamine” in the CTFA dictionary. [0238]
  • (14) Crosslinked methacryloyloxy(C[0239] 1-C4)alkyltri(C1-C4)alkylammonium salt polymers such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo- or copolymerization being followed by crosslinking with a compound containing olefinic unsaturation, in particular methylenebisacrylamide. A crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil can be used more particularly. This dispersion is sold under the name “Salcare® SC 92” by the company Allied Colloids. A crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester can also be used. These dispersions are sold under the names “Salcare® SC 95” and “Salcare® SC 96” by the company Allied Colloids.
  • Other cationic polymers which can be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives. [0240]
  • Among all the cationic polymers which may be used in the context of the present invention, it is preferred to use the polymers of families (1), (9), (10), (11) and (14) and even more preferably the polymers consisting of repeating units of formulae (W) and (U) below: [0241]
    Figure US20040019981A1-20040205-C00009
  • and in particular those whose molecular weight, determined by gel permeation chromatography, is between 9500 and 9900; [0242]
    Figure US20040019981A1-20040205-C00010
  • and in particular those whose molecular weight, determined by gel permeation chromatography, is about 1200. [0243]
  • The concentration of cationic polymer in the composition according to the present invention may range from 0.01% to 10% by weight relative to the total weight of the composition, preferably from 0.05% to 5% and even more preferably from 0.1% to 3%. [0244]
  • Amphoteric Polymers
  • The amphoteric polymers that may be used in accordance with the present invention may be chosen from polymers comprising units K and M randomly distributed in the polymer chain, in which K denotes a unit derived from a monomer comprising at least one basic nitrogen atom and M denotes a unit derived from an acidic monomer comprising one or more carboxylic or sulfonic groups, or alternatively K and M may denote groups derived from zwitterionic carboxybetaine or sulfobetaine monomers; [0245]
  • K and M may also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups bears a carboxylic or sulfonic group linked via a hydrocarbon-based radical, or alternatively K and M form part of a chain of a polymer containing an α,β-dicarboxylic ethylene unit in which one of the carboxylic groups has been made to react with a polyamine comprising one or more primary or secondary amine groups. [0246]
  • The amphoteric polymers corresponding to the above definition that are more particularly preferred are chosen from the following polymers: [0247]
  • (1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, α-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds are described in U.S. Pat. No. 3,836,537. Mention may also be made of the sodium acrylate/acrylamidopropyltrimethylammonium chloride copolymer sold under the name Polyquart KE 3033 by the company Henkel. [0248]
  • The vinyl compound may also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride. The copolymers of acrylic acid and of the latter monomer are sold under the names Merquat 280, Merquat 295 and Merquat Plus 3330 by the company Calgon. [0249]
  • (2) Polymers containing units derived from: [0250]
  • a) at least one monomer chosen from acrylamides and methacrylamides substituted on the nitrogen with an alkyl radical, [0251]
  • b) at least one acidic comonomer containing one or more reactive carboxylic groups, and [0252]
  • c) at least one basic comonomer such as esters containing primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. [0253]
  • The N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides. [0254]
  • The acidic comonomers are chosen more particularly from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid and alkyl monoesters, having 1 to 4 carbon atoms, of maleic or fumaric acids or anhydrides. [0255]
  • The preferred basic comonomers are aminoethyl, butylaminoethyl, N,N′-dimethylaminoethyl and N-tert-butylaminoethyl methacrylates. [0256]
  • The copolymers whose CTFA (4th edition, 1991) name is Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer such as the products sold under the name Amphomer or Lovocryl 47 by the company National Starch are particularly used. [0257]
  • (3) Polyamino amides that are crosslinked and alkylated partially or totally derived from polyamino amides of general formula: [0258]
    Figure US20040019981A1-20040205-C00011
  • in which R[0259] 19 represents a divalent radical derived from a saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid containing an ethylenic double bond, an ester of a lower alkanol, having 1 to 6 carbon atoms, of these acids or a radical derived from the addition of any one of said acids to a bis(primary) or bis(secondary) amine, and Z denotes a bis(primary), mono- or bis(secondary) polyalkylene-polyamine radical and preferably represents:
  • a) in proportions of from 60 to 100 mol %, the radical [0260]
    Figure US20040019981A1-20040205-C00012
  • where x=2 and p=2 or 3, or alternatively x=3 and p=2 [0261]
  • this radical being derived from diethylenetriamine, from triethylenetetraamine or from dipropylenetriamine; [0262]
  • b) in proportions of from 0 to 40 mol %, the radical (XI) above in which x=2 and p=1 and which is derived from ethylenediamine, or the radical derived from piperazine: [0263]
    Figure US20040019981A1-20040205-C00013
  • c) in proportions of from 0 to 20 mol %, the —NH—(CH[0264] 2)6—NH— radical derived from hexamethylenediamine, these polyamino amines being crosslinked by addition of a difunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides and bis-unsaturated derivatives, using from 0.025 to 0.35 mol of crosslinking agent per amine group of the polyamino amide and alkylated by the action of acrylic acid, chloroacetic acid or an alkane sultone, or salts thereof.
  • The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid and acids containing an ethylenic double bond such as, for example, acrylic acid, methacrylic acid and itaconic acid. [0265]
  • The alkane sultones used in the alkylation are preferably propane sultone or butane sultone, and the salts of the alkylating agents are preferably the sodium or potassium salts. [0266]
  • (4) Polymers containing zwitterionic units of formula: [0267]
    Figure US20040019981A1-20040205-C00014
  • in which R[0268] 20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, R21 and R22 represent a hydrogen atom, methyl, ethyl or propyl, R23 and R24 represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R23 and R24 does not exceed 10.
  • The polymers comprising such units can also contain units derived from nonzwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate. [0269]
  • By way of example, mention may be made of the copolymer of butyl methacrylate/dimethyl carboxymethylammonio ethyl methacrylate such as the product sold under the name Diaformer Z301 by the company Sandoz. [0270]
  • (5) Polymers derived from chitosan, described especially in French patent No 2 137 684 or U.S. Pat. No. 3,879,376, containing monomer units corresponding to formulae (XIII), (XIV) and (XV) below connected in their chain: [0271]
    Figure US20040019981A1-20040205-C00015
  • the unit (XIII) being present in proportions of between 0 and 30%, the unit (XIV) in proportions of between 5 and 50% and the unit (XV) in proportions of between 30 and 90%, it being understood that, in this unit (XV), R[0272] 25 represents a radical of formula:
    Figure US20040019981A1-20040205-C00016
  • in which q denotes zero or 1; [0273]
  • if q=0, R[0274] 26, R27 and R28, which may be identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue which are optionally interrupted by one or more nitrogen atoms and/or optionally substituted with one or more amine, hydroxyl, carboxyl, alkylthio or sulfonic groups, an alkylthio residue in which the alkyl group bears an amino residue, at least one of the radicals R26, R27 and R28 being, in this case, a hydrogen atom;
  • or, if q=1, R[0275] 26, R27 and R28 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.
  • (6) Polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan sold under the name “Evalsan” by the company Jan Dekker. [0276]
  • (7) Polymers corresponding to the general formula (XI) as described, for example, in French patent 1 400 366: [0277]
    Figure US20040019981A1-20040205-C00017
  • in which R[0278] 29 represents a hydrogen atom, a CH3O, CH3CH2O or phenyl radical, R30 denotes hydrogen or a lower alkyl radical such as methyl or ethyl, R31 denotes hydrogen or a lower alkyl radical such as methyl or ethyl, R32 denotes a lower alkyl radical such as methyl or ethyl or a radical corresponding to the formula: —R33—N(R31)2, R33 representing a —CH2—CH2—, —CH2—CH2—CH2— or —CH2—CH(CH3)— group, R31 having the meanings mentioned above,
  • as well as the higher homologs of these radicals and containing up to 6 carbon atoms, [0279]
  • r is such that the molecular weight is between 500 and 6 000 000 and preferably between 1000 and 1 000 000. [0280]
  • (8) Amphoteric polymers of the type —D—X—D—X— chosen from: [0281]
  • a) polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds containing at least one unit of formula: [0282]
  • —D—X—D—X—D—  (XVII)
  • where D denotes a radical [0283]
    Figure US20040019981A1-20040205-C00018
  • X denotes the symbol E or E′, E or E′, which may be identical or different, denotes a divalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with hydroxyl groups and which can contain, in addition to the oxygen, nitrogen and sulfur atoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups; [0284]
  • b) polymers of formula: [0285]
  • —D—X—D—X—  (XVIII)
  • where D denotes a radical [0286]
    Figure US20040019981A1-20040205-C00019
  • and X denotes the symbol E or E′ and at least once E′; E having the meaning given above and E′ being a divalent radical which is an alkylene radical with a straight or branched chain having up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with one or more hydroxyl radicals and containing one or more nitrogen atoms, the nitrogen atom being substituted with an alkyl chain which is optionally interrupted by an oxygen atom and necessarily containing one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloroacetic acid or sodium chloroacetate. [0287]
  • (9) (C[0288] 1-C5)alkyl vinyl ether/maleic anhydride copolymers partially modified by semiamidation with an N,N-dialkylaminoalkylamine such as N,N-dimethylaminopropylamine or by semiesterification with an N,N-dialkanolamine. These copolymers can also contain other vinyl comonomers such as vinylcaprolactam.
  • The amphoteric polymers that are particularly preferred according to the invention are those of family (1). [0289]
  • According to the invention, the amphoteric polymer(s) may represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight and even more preferably from 0.1% to 3% by weight relative to the total weight of the composition. [0290]
  • The compositions of the invention preferably comprise one or more surfactants. [0291]
  • The surfactant(s) can be chosen without preference, alone or as mixtures, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants. [0292]
  • The surfactants that are suitable for carrying out the present invention are, in particular, the following: [0293]
  • (i) Anionic surfactant(s): [0294]
  • As examples of anionic surfactants which can be used, alone or as mixtures, in the context of the present invention, mention may be made in particular (nonlimiting list) of salts (in particular alkaline salts, especially sodium salts, ammonium salts, amine salts, amino alcohol salts or magnesium salts) of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylarylpolyether sulfates, monoglyceride sulfates; alkyl sulfonates, alkyl phosphates, alkylamide sulfonates, alkylaryl sulfonates, α-olefin sulfonates, paraffin sulfonates; (C[0295] 6-C24) alkyl sulfosuccinates, (C6-C24) alkyl ether sulfosuccinates, (C6-C24) alkylamide sulfosuccinates; (C6-C24) alkyl sulfoacetates; (C6-C24) acyl sarcosinates and (C6-C24) acyl glutamates. It is also possible to use the carboxylic esters of (C6-C24) alkylpolyglycosides, such as alkylglucoside citrates, alkylpolyglycoside tartrates and alkylpolyglycoside sulfosuccinates, alkylsulfosuccinamates; acyl isethionates and N-acyltaurates, the alkyl or acyl radical of all of these various compounds preferably containing from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group. Among the anionic surfactants which can also be used, mention may also be made of fatty acid salts such as the salts of oleic, ricinoleic, palmitic and stearic acids, coconut oil acid or hydrogenated coconut oil acid; acyl lactylates in which the acyl radical contains 8 to 20 carbon atoms. Alkyl-D-galactosideuronic acids and their salts, polyoxyalkylenated (C6-C24) alkyl ether carboxylic acids, polyoxyalkylenated (C6-C24) alkylaryl ether carboxylic acids, polyoxyalkylenated (C6-C24) alkylamido ether carboxylic acids and their salts, in particular those containing from 2 to 50 alkylene oxide, in particular ethylene oxide, groups, and mixtures thereof can also be used.
  • (ii) Nonionic surfactant(s): [0296]
  • The nonionic surfactants are also compounds that are well known per se (see in particular in this respect “Handbook of Surfactants” by M. R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp. 116-178) and, in the context of the present invention, their nature is not a critical feature. Thus, they can be chosen in particular from (nonlimiting list) polyethoxylated or polypropoxylated alkylphenols, α-diols or alcohols having a fatty chain containing, for example, 8 to 18 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range in particular from 2 to 50. Mention may also be made of copolymers of ethylene oxide and of propylene oxide, condensates of ethylene oxide and of propylene oxide with fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 mol of ethylene oxide, polyglycerolated fatty amides containing on average 1 to 5, and in particular 1.5 to 4, glycerol groups; polyethoxylated fatty amines preferably having from 2 to 30 mol of ethylene oxide; oxyethylenated fatty acid esters of sorbitan having from 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkylpolyglycosides, N-alkylglucamine derivatives, amine oxides such as (C[0297] 10-C14)alkylamine oxides or N-acylaminopropylmorpholine oxides. It will be noted that the alkylpolyglycosides constitute nonionic surfactants that are particularly suitable in the context of the present invention.
  • (iii) Amphoteric or zwitterionic surfactant(s): [0298]
  • The amphoteric or zwitterionic surfactants, whose nature is not a critical feature in the context of the present invention, can be, in particular (nonlimiting list), aliphatic secondary or tertiary amine derivatives in which the aliphatic radical is a linear or branched chain containing 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulfonate, sulfate, phosphate or phosphonate); mention may also be made of (C[0299] 8-C20)alkylbetaines, sulfobetaines, (C8-C20)alkylamido(C1-C6)alkylbetaines or (C8-C20)alkylamido(C1-C6)alkylsulfobetaines.
  • Among the amine derivatives, mention may be made of the products sold under the name Miranol, as described in U.S. Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names amphocarboxyglycinates and amphocarboxypropionates of respective structures: [0300]
  • R2—CONHCH2CH2—N (R3) (R4) (CH2COO)
  • in which: R[0301] 2 denotes an alkyl radical of an acid R2—COOH present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl radical, R3 denotes a β-hydroxyethyl group and R4 denotes a carboxymethyl group;
  • and [0302]
  • R2′—CONHCH2CH2—N (B) (C)
  • in which: [0303]
  • B represents —CH[0304] 2CH2OX′, C represents —(CH2)z—Y′, with z=1 or 2,
  • X′ denotes a —CH[0305] 2CH2—COOH group or a hydrogen atom,
  • Y′ denotes —COOH or a —CH[0306] 2—CHOH—SO3H radical,
  • R[0307] 2′ denotes an alkyl radical of an acid R9—COOH present in coconut oil or in hydrolyzed linseed oil, an alkyl radical, in particular a C7, C9, C11 or C13 alkyl radical, a C17 alkyl radical and its iso form, an unsaturated C17 radical.
  • These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid. [0308]
  • By way of example, mention may be made of the cocoamphodiacetate sold under the trade name Miranol® C2M Concentrate by the company Rhodia Chimie. [0309]
  • (iv) Cationic surfactants: [0310]
  • Among the cationic surfactants that may be mentioned in particular (nonlimiting list) are: primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated; quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium chlorides or bromides; imidazoline derivatives; or amine oxides of cationic nature. [0311]
  • The amounts of surfactants present in the composition according to the invention can range from 0.01% to 40% and preferably from 0.5% to 30% relative to the total weight of the composition. [0312]
  • The compositions according to the invention can also contain other agents for adjusting the rheology, such as cellulose-based thickeners (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, etc.), guar gum and its derivatives (hydroxypropyl guar, etc.), gums of microbial origin (xanthan gum, scleroglucan gum, etc.), synthetic thickeners such as crosslinked acrylic acid or acrylamidopropanesulfonic acid homopolymers and ionic or nonionic associative polymers such as the polymers sold under the names Pemulen TR1 or TR2 by the company Goodrich, Salcare SC90 by the company Allied Colloids, Aculyn 22, 28, 33, 44 or 46 by the company Rohm & Haas, and Elfacos T210 and T212 by the company Akzo. [0313]
  • These additional thickeners can represent from 0.01% to 10% by weight relative to the total weight of the composition. [0314]
  • The medium of the composition that is suitable for dyeing is preferably an aqueous medium consisting of water and may advantageously contain cosmetically acceptable organic solvents including, more particularly, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, or glycols or glycol ethers such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol and diethylene glycol alkyl ethers such as, for example, diethylene glycol monoethyl ether or monobutyl ether. The solvents may then be present in concentrations of between about 0.5% and 20% and preferably between about 2% and 10% by weight relative to the total weight of the composition. [0315]
  • Composition A may also comprise an effective amount of other agents, which are previously known elsewhere for direct dyeing, such as various common adjuvants, for instance sequestering agents such as EDTA and etidronic acid, UV screening agents, waxes, volatile or nonvolatile, cyclic or linear or branched silicones, which are possibly organomodified (especially with amine groups), preserving agents, ceramides, pseudoceramides, plant, mineral or synthetic oils, vitamins or provitamins, for instance panthenol, opacifiers, associative polymers other than those of the invention, and in particular nonionic associative polyurethane polyethers. [0316]
  • Needless to say, a person skilled in the art will take care to select the optional additional compound(s) mentioned above such that the advantageous properties intrinsically associated with the dye composition according to the invention are not, or are not substantially, adversely affected by the envisaged addition(s). [0317]
  • In the ready-to-use composition with oxidizing agent, the oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, and persalts such as perborates and persulfates. It is particularly preferred to use hydrogen peroxide. This oxidizing agent advantageously consists of an aqueous hydrogen peroxide solution whose titer may range, more particularly, from about 1 to 40 volumes and even more preferably from about 5 to 40 volumes. [0318]
  • Oxidizing agents that may also be used are one or more redox enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase), where appropriate in the presence of their respective donor or cofactor. [0319]
  • The pH of the ready-to-use composition [oxidant-free ready-to-use composition or composition resulting from mixing the dye composition A1 and the oxidizing composition B1] is generally between the values 2 and 12. It is preferably between 3 and 11, and may be adjusted to the desired value by means of acidifying or basifying agents that are well known in the prior art in the dyeing of keratin fibers. [0320]
  • More preferentially, when the composition contains an oxidizing agent to lighten the fibers, the pH of the ready-to-use mixture is greater than 7 and even more preferentially greater than 8. [0321]
  • Among the basifying agents that may be mentioned, for example, are aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine and also derivatives thereof, oxyethylenated and/or oxypropylenated hydroxyalkylamines and ethylenediamines, sodium hydroxide, potassium hydroxide and the compounds of formula (XIX) below: [0322]
    Figure US20040019981A1-20040205-C00020
  • in which R is a propylene residue optionally substituted with a hydroxyl group or a C[0323] 1-C4 alkyl radical; R38, R39, R40 and R41, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.
  • The acidifying agents are conventionally, for example, mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, carboxylic acids, for instance tartaric acid, citric acid or lactic acid, or sulfonic acids. [0324]
  • The dyeing process according to the invention preferably consists in applying the oxidant-free ready-to-use composition A or the composition prepared extemporaneously at the time of use from compositions A1 and B1 described above, to wet or dry keratin fibers, and leaving the composition to act for an action time preferably ranging from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, rinsing the fibers and then optionally washing them with shampoo, followed by rinsing them again and drying them. [0325]
  • One variant of this process consists in taking a composition A′ comprising at least one direct dye but without cationic associative polyurethane, and a composition A″ comprising at least one cationic associative polyurethane polymer, and mixing, at the time of use, these compositions A′ and A″ with oxidizing composition B, followed by applying the mixture obtained and leaving it to act as previously. [0326]
  • Concrete examples illustrating the invention are given below, without, however, having any limiting nature.[0327]
  • EXAMPLE 1
  • The following compositions were prepared: [0328]
  • (amounts expressed in grams) [0329]
    Oxidizing composition:
    Fatty alcohol 2.3
    Oxyethylenated fatty alcohol 0.6
    Fatty amide 0.9
    Glycerol 0.5
    Hydrogen peroxide 7.5
    Fragrance qs
    Demineralized water qs 100
  • [0330]
    Dye composition:
    A B
    Oxyethylenated fatty alcohols 32.5 32.5
    Oleic acid 2 2
    Oleyl alcohol 1.8 1.8
    Fatty amide 4 4
    Glycerol 3 3
    Cationic polymer of formula (W) as a 1.2 AM* 1.2 AM*
    60% solution in water
    Merquat 280 2 2
    Sequestering agent Qs qs
    Reducing agent Qs qs
    Aqueous ammonia (20% NH3) 8 8
    Diamino-1,4-nitro-2- 0.6 0.6
    benzene
    Polymer 1 0.3 AM*
    Polymer 2 0.3 AM*
    Water qs 100 g 100 g
  • Polymer 1 is the following polymer: [0331]
  • C18H37—O—CONHR4NHCO—O—(CH2)2—N+(CH3) (CH3)—(CH2)2—O—CONHR2NHCO—O(POE)O—CONHR2NHCO—O—(CH2)2—N+(CH3) (CH3)—(CH2)2—O—CONHR4NHCO—OC18H37
  • with: [0332]
  • R[0333] 4 =methylenedicyclohexyl
  • counterion: CH[0334] 3SO4
  • It is synthesized from the following reagents: [0335]
    C18H37OH 2 Mol
    Methylenedicyclohexyl diisocyanate 4 Mol
    Polyethylene glycol 1 Mol
    N-Methylethanolamine 2 Mol
    Quaternizing agent (CH3)2SO4 2 Mol
  • Polymer 2 is the following polymer: [0336]
  • C18H37N+(CH3) (CH3)—(CH2)2—O—CONHR4NHCO—O(POE)O—CONHR4NHCO—O—(CH2)2—N+(CH3) (CH3)C18H37
  • with: [0337]
  • R[0338] 4=methylenedicyclohexyl
  • counterion: Cl[0339]
  • It is synthesized from the following reagents: [0340]
    Methylenedicyclohexyl diisocyanate 2 Mol
    Polyethylene glycol 1 Mol
    N,N-Dimethylethanolamine 2 Mol
    Quaternizing agent C18H37OH 2 Mol
  • The dye compositions were mixed, at the time of use, in a plastic bowl for 2 minutes, with the oxidizing composition given above, in a proportion of 1 part of dye composition per 1.5 parts of oxidizing composition. [0341]
  • The mixtures obtained were applied to locks of natural hair containing 90% white hairs, and were left to act on the locks for 30 minutes. [0342]
  • The locks were then rinsed with water, washed with standard shampoo, rinsed again with water and then dried and disentangled. [0343]
  • The hair was dyed in both cases in a strong red shade. [0344]
  • EXAMPLE 2
  • The composition below was prepared: [0345]
  • (expressed in grams) [0346]
    Oxyethylenated fatty alcohols 32.5
    Oleic acid 2
    Oleyl alcohol 1.8
    Fatty amide 4
    Glycerol 3
    Basic Red 76 0.4
    Polymer 1 0.3 AM*
    2-Amino-2-methyl-1-propanol qs PH 8.5
    Water qs 100
  • This composition was applied for 30 minutes to gray hair containing 90% white hairs. After rinsing and drying, the hair was dyed a strong red. [0347]

Claims (37)

1. A direct dye composition for keratin fibers, in particular for human keratin fibers and more particularly the hair, comprising, in a medium that is suitable for dyeing, at least one direct dye, which is characterized in that it also comprises at least one cationic associative polyurethane.
2. The composition as claimed in claim 1, characterized in that the cationic associative polyurethane is of formula (Ia) below:
R—X—(P)n—[L—(Y)m]r—L′—(P′)p—X′—R′  (Ia)
in which:
R and R′, which may be identical or different, represent a hydrophobic group or a hydrogen atom;
X and X′, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively a group L″;
L, L′ and L″, which may be identical or different, represent a group derived from a diisocyanate;
P and P′, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group;
Y represents a hydrophilic group;
r is an integer between 1 and 100, preferably between 1 and 50 and in particular between 1 and 25,
n, m and p each range, independently of each other, from 0 to 1000;
the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
3. The composition as claimed in claim 2, characterized in that R and R′ both independently represent a hydrophobic group, X and X′ each represent a group L″, n and p are between 1 and 1000, and L, L′, L″, P, P′, Y and m have the meaning given in claim 2.
4. The composition as claimed in claim 2, characterized in that R and R′ both independently represent a hydrophobic group, X and X′ both independently represent a group comprising a quaternary amine, n and p are zero, and L, L′, Y and m have the meaning given in claim 2.
5. The composition as claimed in any one of claims 2 to 4, characterized in that R and R′ represent a radical or polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, in which one or more of the carbon atoms may be replaced with a hetero atom chosen from S, N, O and P, or a radical or polymer containing a perfluoro or silicone chain.
6. The composition as claimed in any one of claims 2 to 5, characterized in that X and X′ represent one of the formulae:
Figure US20040019981A1-20040205-C00021
in which:
R2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a hetero atom chosen from N, S, O and P;
R1 and R3, which may be identical or different, denote a linear or branched C1-C30 alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a hetero atom chosen from N, S, O and P;
Ais a physiologically acceptable counterion.
7. The composition as claimed in any one of claims 2 to 6, characterized in that the groups L, L′ and L″, which may be identical or different, represent the formula:
Figure US20040019981A1-20040205-C00022
in which:
Z represents —O—, —S— or —NH—; and
R4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a hetero atom chosen from N, S, O and P.
8. The composition as claimed in any one of claims 2 to 7, characterized in that the groups P and P′, which may be identical or different, represent at least one of the following formulae:
Figure US20040019981A1-20040205-C00023
in which:
R5 and R7 have the same meanings as R2;
R6, R8 and R9 have the same meanings as R1 and R3;
R10 represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more hetero atoms chosen from N, O, S and P; and
Ais a physiologically acceptable counterion.
9. The composition as claimed in any one of claims 2 to 8, characterized in that Y represents a group derived from ethylene glycol, from diethylene glycol or from propylene glycol, or a group derived from a polymer chosen from polyethers, sulfonated polyesters and sulfonated polyamides.
10. The composition as claimed in any one of the preceding claims, characterized in that the cationic associative polyurethanes have a number-average molecular mass of between 400 and 500 000, preferably between 1000 and 400 000 and in particular between 1000 and 300 000.
11. The composition as claimed in any one of the preceding claims, characterized in that the cationic associative polyurethanes are used in an amount ranging from 0.01% to 10% by weight relative to the total weight of the composition.
12. The composition as claimed in claim 11, characterized in that the cationic associative polyurethanes are used in an amount ranging from 0.1% to 5% by weight relative to the total weight of the composition.
13. The composition as claimed in any one of the preceding claims, characterized in that the direct dye is chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, neutral, acidic or cationic quinone, and in particular anthraquinone, direct dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
14. The composition as claimed in any one of the preceeding claims, characterized in that the direct dye(s) are present in concentrations ranging from 0.001% to 20% and preferably from 0.005% to 10% by weight relative to the total weight of the composition.
15. The composition as claimed in any one of the preceding claims, characterized in that it also contains at least one amphoteric substantive polymer or cationic substantive polymer other than the cationic associative polyurethanes described in any one of claims 2 to 12.
16. The composition as claimed in claim 15, characterized in that the cationic polymer is a polyquaternary ammonium polymer consisting of repeating units corresponding to formula (W) below:
Figure US20040019981A1-20040205-C00024
17. The composition as claimed in claim 15, characterized in that the cationic polymer is a polyquaternary ammonium polymer consisting of repeating units corresponding to formula (U) below:
Figure US20040019981A1-20040205-C00025
18. The composition as claimed in claim 15, characterized in that the amphoteric polymer is a copolymer comprising at least, as monomers, acrylic acid and a dimethyldiallylammonium salt.
19. The composition as claimed in any one of claims 15 to 18, characterized in that the cationic or amphoteric polymer(s) represent(s) from 0.01% to 10%, preferably from 0.05% to 5% and even more preferably from 0.1% to 3% by weight, relative to the total weight of the composition.
20. The composition as claimed in any one of the preceding claims, characterized in that it contains at least one surfactant chosen from anionic, cationic, nonionic and amphoteric surfactants.
21. The composition as claimed in claim 20, characterized in that the surfactants represent from 0.01% to 40% and preferably from 0.5% to 30% by weight, relative to the total weight of the composition.
22. The composition as claimed in any one of the preceding claims, characterized in that it contains at least one additional thickener.
23. The composition as claimed in claim 22, characterized in that the additional thickener is a cellulose derivative, a guar derivative, a gum of microbial origin or a synthetic thickener.
24. The composition as claimed in claim 23, characterized in that the additional thickeners represent from 0.01% to 10% by weight, relative to the total weight of the ready-to-use composition.
25. The composition as claimed in any one of the preceding claims, characterized in that it has a pH ranging from 2 to 12.
26. The ready-to-use composition as claimed in any one of the preceding claims, characterized in that it also contains an oxidizing agent.
27. The composition as claimed in claim 26, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, persalts, and redox enzymes, optionally with their respective donor or cofactor.
28. The composition as claimed in claim 27, characterized in that the oxidizing agent is hydrogen peroxide.
29. The composition as claimed in claim 28, characterized in that it is an aqueous hydrogen peroxide solution whose titer ranges from 1 to 40 volumes.
30. The composition as claimed in any one of claims 26 to 29, characterized in that it has a pH of greater than 7 and preferably greater than 8.
31. A process for the direct dyeing of keratin fibers, in particular human keratin fibers and more particularly the hair, characterized in that it consists in applying to the fibers a dye composition A as defined in any one of claims 1 to 25.
32. A process for the lightening direct dyeing of keratin fibers and in particular of human keratin fibers and more particularly the hair, characterized in that it consists in applying to the fibers a composition resulting from the extemporaneous mixing of a composition A1 comprising, in a medium that is suitable for dyeing, at least one direct dye, and of an oxidizing composition B1 comprising an oxidizing agent, composition A1 and/or composition B1 comprising at least one cationic associative polyurethane as defined in any one of claims 1 to 12.
33. The process as claimed in claim 31 or 32, characterized in that it consists in applying the ready-to-use composition A or that prepared extemporaneously at the time of use from compositions A1 and B1 described above, to wet or dry keratin fibers, leaving the composition to act for an action time ranging from 1 to 60 minutes approximately and preferably from 10 to 45 minutes, rinsing the fibers and then optionally washing them with shampoo, followed by rinsing them again and drying them.
34. A process for the lightening direct dyeing of keratin fibers, in particular for human keratin fibers and more particularly the hair, characterized in that it consists in applying the ready-to-use composition prepared extemporaneously at the time of use from a composition A′ comprising at least one direct dye, but without cationic associative polyurethane defined in claims 1-12, another composition A″ comprising at least one cationic associative polyurethane defined as claimed in claims 1 to 12, and an oxidizing composition B, to the wet or dry keratin fibers, leaving the composition to act for an action time ranging from 1 to 60 minutes approximately and preferably from 10 to 45 minutes, rinsing the fibers and then optionally washing them with shampoo, followed by rinsing them again and drying them.
35. The dyeing process as claimed in any one of claims 31-34, characterized in that composition A or A1 and/or composition B1 comprise at least one cationic or amphoteric substantive polymer and at least one surfactant.
36. A two-compartment device or “kit” for the direct dyeing of human keratin fibers, and more particularly the hair, characterized in that one compartment contains a composition comprising at least one direct dye, and another compartment contains a composition comprising at least one cationic associative polyurethane as defined in any one of claims 1 to 12.
37. A two-compartment device or “kit” for the lightening direct dyeing of human keratin fibers, and more particularly the hair, characterized in that one compartment contains a composition A1 comprising, in a medium that is suitable for dyeing, at least one direct dye, and another compartment contains a composition B1 comprising an oxidizing agent, at least one cationic associative polyurethane being present in the composition A1 or in the composition B1, or in each of the compositions A1 and B1.
US10/415,954 2000-11-08 2001-11-06 Direct dyeing composition for keratinous fibres comprising a cationic associative polyurethane Expired - Fee Related US7108726B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR00/14322 2000-11-08
FR0014322A FR2816208B1 (en) 2000-11-08 2000-11-08 DIRECT DYE COMPOSITION FOR KERATINIC FIBERS COMPRISING A CATIONIC ASSOCIATIVE POLYURETHANE
PCT/FR2001/003427 WO2002038115A1 (en) 2000-11-08 2001-11-06 Direct dyeing composition for keratinous fibres comprising a cationic associative polyurethane

Publications (2)

Publication Number Publication Date
US20040019981A1 true US20040019981A1 (en) 2004-02-05
US7108726B2 US7108726B2 (en) 2006-09-19

Family

ID=8856187

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/415,954 Expired - Fee Related US7108726B2 (en) 2000-11-08 2001-11-06 Direct dyeing composition for keratinous fibres comprising a cationic associative polyurethane

Country Status (10)

Country Link
US (1) US7108726B2 (en)
EP (1) EP1335694B1 (en)
JP (1) JP2004513138A (en)
AR (1) AR031302A1 (en)
AT (1) ATE339992T1 (en)
AU (1) AU2002223757A1 (en)
DE (1) DE60123268T2 (en)
ES (1) ES2271107T3 (en)
FR (1) FR2816208B1 (en)
WO (1) WO2002038115A1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040205902A1 (en) * 2002-12-06 2004-10-21 Francois Cottard Composition for the oxidation dyeing of keratin fibers, comprising at least one non-oxyalkenylated fatty alcohol, at least one oxidation dye, at least one associative polymer, and at least one amide of an alkanolamine and a C14-C30 fatty acid
US20040258641A1 (en) * 2003-04-01 2004-12-23 Gregory Plos Cosmetic composition for dyeing human keratin materials, comprising at least one fluorescent dye and at least one cationic polymer, and a dyeing process therefor
US20040256598A1 (en) * 2003-04-01 2004-12-23 Gregory Plos Composition for dyeing human keratin materials, comprising at least one fluorescent dye and at least one compound comprising an acid functional group and processes therefor
US20050005368A1 (en) * 2003-04-01 2005-01-13 Gregory Plos Process for dyeing, with a lightening effect, human keratin fibers that have been permanently reshaped, using at least one composition comprising at least one fluorescent dye
US20050008594A1 (en) * 2003-04-01 2005-01-13 Gregory Plos Composiiton for dyeing human keratin materials, comprising at least one fluorescent dye and at least one polyol, process therefor and use thereof
US20050008593A1 (en) * 2003-04-01 2005-01-13 Gregory Plos Dye composition comprising at least one fluorescent dye and a non-associative thickening polymer for human keratin materials, process therefor, and method thereof
US20050005371A1 (en) * 2003-04-01 2005-01-13 Chrystel Pourille-Grethen Method of dyeing human keratin materials with a lightening effect with compositions comprising at least one fluorescent dye and at least one amphoteric or nonionic surfactant, composition thereof, process thereof, and device therefor
US20050028301A1 (en) * 2001-09-28 2005-02-10 Florent Pastore Dyeing composition with a brightening effect for human kerationous fibres
US20050031562A1 (en) * 2003-04-01 2005-02-10 Luc Gourlaouen Composition for dyeing human keratin materials, comprising at least one fluorescent dye and at least one associative polymer, process therefor and use thereof
US20050076457A1 (en) * 2003-04-01 2005-04-14 Gregory Plos Composition for dyeing a human keratin material, comprising at least one fluorescent dye and at least one insoluble conditioning agent, process thereof, use thereof, and devices thereof
US20050098763A1 (en) * 2003-04-01 2005-05-12 Gregory Plos Composition for dyeing human keratin materials, comprising a fluorescent dye and a particular sequestering agent, process therefor and use thereof
US20060010617A1 (en) * 2002-12-24 2006-01-19 Luc Gourlaouen Method for dyeing or coloring human keratin materials with lightening effect using a composition comprising at least one fluorescent compound and at least one optical brightener
US20090288674A1 (en) * 2003-04-01 2009-11-26 L'oreal S.A. Cosmetic dye composition with a lightening effect for human keratin materials, comprising at least one fluorescent dye and at least one aminosilicone, and process of dyeing

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040200011A1 (en) 2002-12-06 2004-10-14 Luc Nicolas-Morgantini Composition for the oxidation dyeing of keratin fibers, comprising at least one oxidation dye, at least one fatty alcohol, at least one associative polymer, and at least one C14-C30 alkyl sulphate
FR2848105B1 (en) * 2002-12-06 2006-11-17 Oreal OXIDATION DYEING COMPOSITION FOR KERATIN FIBERS COMPRISING FATTY ALCOHOL, OXIDATION DYE, ASSOCIATIVE POLYMER, AND C14-C30 ALKYL SULFATE
FR2848106B1 (en) * 2002-12-06 2006-11-17 Oreal DYEING COMPOSITION FOR KERATIN FIBERS COMPRISING NON-OXYALKYLENE FATTY ALCOHOL, OXIDATION DYE, ASSOCIATIVE POLYMER, AND AMIDE OF ALKANOLAMINE AND C14-C30 FATTY ACID
FR2853240A1 (en) * 2003-04-01 2004-10-08 Oreal COLORING COMPOSITION FOR HUMAN KERATINIC MATERIALS COMPRISING A FLUORESCENT COLORANT AND AN ASSOCIATIVE POLYMER, PROCESS AND USE
JP2005232021A (en) * 2004-02-17 2005-09-02 Kanebo Ltd Hair dye
FR2984731B1 (en) * 2011-12-21 2013-12-20 Oreal PROCESS FOR COLORING OR LIGHTENING TWO-PART KERATIN FIBERS FROM DIRECT OIL-RICH EMULSION BASED ON THERMO-THICKENING POLYMER AND SOLID FATTY ALCOHOL
FR2984737B1 (en) * 2011-12-21 2013-12-20 Oreal PROCESS FOR COLORING OR LIGHTENING TWO-PART KERATIN FIBERS FROM AN OIL-RICH ALKALINE DIRECT EMULSION BASED ON SOLID NONIONIC SURFACTANT AND THERMO-THICKENING POLYMER
EP3490102B1 (en) 2013-03-15 2020-08-05 Tc1 Llc Malleable tets coil with improved anatomical fit
EP3681921A2 (en) * 2017-09-13 2020-07-22 Living Proof, Inc. Color protectant compositions

Citations (88)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2261002A (en) * 1941-06-17 1941-10-28 Du Pont Organic nitrogen compounds
US2271378A (en) * 1939-08-30 1942-01-27 Du Pont Pest control
US2273780A (en) * 1939-12-30 1942-02-17 Du Pont Wax acryalte ester blends
US2375853A (en) * 1942-10-07 1945-05-15 Du Pont Diamine derivatives
US2388614A (en) * 1942-05-05 1945-11-06 Du Pont Disinfectant compositions
US2454547A (en) * 1946-10-15 1948-11-23 Rohm & Haas Polymeric quaternary ammonium salts
US2528378A (en) * 1947-09-20 1950-10-31 John J Mccabe Jr Metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same
US2781354A (en) * 1956-03-26 1957-02-12 John J Mccabe Jr Imidazoline derivatives and process
US2961347A (en) * 1957-11-13 1960-11-22 Hercules Powder Co Ltd Process for preventing shrinkage and felting of wool
US3206462A (en) * 1962-10-31 1965-09-14 Dow Chemical Co Quaternary poly(oxyalkylene)alkylbis(diethylenetriamine) compounds
US3227615A (en) * 1962-05-29 1966-01-04 Hercules Powder Co Ltd Process and composition for the permanent waving of hair
US3472840A (en) * 1965-09-14 1969-10-14 Union Carbide Corp Quaternary nitrogen-containing cellulose ethers
US3589578A (en) * 1968-01-20 1971-06-29 Monforts Fa A Tension-relieving device for stretchable sheet material
US3632559A (en) * 1967-09-28 1972-01-04 Sandoz Ltd Cationically active water soluble polyamides
US3836537A (en) * 1970-10-07 1974-09-17 Minnesota Mining & Mfg Zwitterionic polymer hairsetting compositions and method of using same
US3874870A (en) * 1973-12-18 1975-04-01 Mill Master Onyx Corp Microbiocidal polymeric quarternary ammonium compounds
US3879376A (en) * 1971-05-10 1975-04-22 Oreal Chitosan derivative, method of making the same and cosmetic composition containing the same
US3910862A (en) * 1970-01-30 1975-10-07 Gaf Corp Copolymers of vinyl pyrrolidone containing quarternary ammonium groups
US3912808A (en) * 1970-02-25 1975-10-14 Gillette Co Hair waving and straightening process and composition containing water-soluble amino and quaternary ammonium polymers
US3917817A (en) * 1971-11-29 1975-11-04 Oreal Hair treating cosmetic compositions containing piperazine based cationic polymer
US3929990A (en) * 1973-12-18 1975-12-30 Millmaster Onyx Corp Microbiocidal polymeric quaternary ammonium compounds
US3966904A (en) * 1974-10-03 1976-06-29 Millmaster Onyx Corporation Quaternary ammonium co-polymers for controlling the proliferation of bacteria
US4001432A (en) * 1974-10-29 1977-01-04 Millmaster Onyx Corporation Method of inhibiting the growth of bacteria by the application thereto of capped polymers
US4003699A (en) * 1974-11-22 1977-01-18 Henkel & Cie G.M.B.H. Oxidation hair dyes based upon tetraaminopyrimidine developers
US4005193A (en) * 1974-08-07 1977-01-25 Millmaster Onyx Corporation Microbiocidal polymeric quaternary ammonium compounds
US4013787A (en) * 1971-11-29 1977-03-22 Societe Anonyme Dite: L'oreal Piperazine based polymer and hair treating composition containing the same
US4025627A (en) * 1973-12-18 1977-05-24 Millmaster Onyx Corporation Microbiocidal polymeric quaternary ammonium compounds
US4025653A (en) * 1975-04-07 1977-05-24 Millmaster Onyx Corporation Microbiocidal polymeric quaternary ammonium compounds
US4025617A (en) * 1974-10-03 1977-05-24 Millmaster Onyx Corporation Anti-microbial quaternary ammonium co-polymers
US4027008A (en) * 1975-05-14 1977-05-31 The Gillette Company Hair bleaching composition containing water-soluble amino and quaternary ammonium polymers
US4027020A (en) * 1974-10-29 1977-05-31 Millmaster Onyx Corporation Randomly terminated capped polymers
US4026945A (en) * 1974-10-03 1977-05-31 Millmaster Onyx Corporation Anti-microbial quaternary ammonium co-polymers
US4031025A (en) * 1971-05-10 1977-06-21 Societe Anonyme Dite: L'oreal Chitosan derivative, sequestering agents for heavy metals
US4031307A (en) * 1976-05-03 1977-06-21 Celanese Corporation Cationic polygalactomannan compositions
US4131576A (en) * 1977-12-15 1978-12-26 National Starch And Chemical Corporation Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system
US4157388A (en) * 1977-06-23 1979-06-05 The Miranol Chemical Company, Inc. Hair and fabric conditioning compositions containing polymeric ionenes
US4165367A (en) * 1977-06-10 1979-08-21 Gaf Corporation Hair preparations containing vinyl pyrrolidone copolymer
US4172887A (en) * 1973-11-30 1979-10-30 L'oreal Hair conditioning compositions containing crosslinked polyaminopolyamides
US4189468A (en) * 1973-11-30 1980-02-19 L'oreal Crosslinked polyamino-polyamide in hair conditioning compositions
US4197865A (en) * 1975-07-04 1980-04-15 L'oreal Treating hair with quaternized polymers
US4217914A (en) * 1974-05-16 1980-08-19 L'oreal Quaternized polymer for use as a cosmetic agent in cosmetic compositions for the hair and skin
US4223009A (en) * 1977-06-10 1980-09-16 Gaf Corporation Hair preparation containing vinyl pyrrolidone copolymer
US4240450A (en) * 1977-03-15 1980-12-23 L'oreal Composition and process for the treatment of keratin materials with polymers
US4277581A (en) * 1973-11-30 1981-07-07 L'oreal Polyamino-polyamide crosslinked with crosslinking agent
US4348202A (en) * 1978-06-15 1982-09-07 L'oreal Hair dye or bleach supports
US4349532A (en) * 1977-09-20 1982-09-14 Guy Vanlerberghe Cosmetic compositions based on poly-(quaternary ammonium) polymers
US4381919A (en) * 1975-07-04 1983-05-03 Societe Anonyme Dite: L'oreal Hair dye composition containing quaternized polymers
US4422853A (en) * 1974-05-16 1983-12-27 L'oreal Hair dyeing compositions containing quaternized polymer
US4591610A (en) * 1983-03-23 1986-05-27 L'oreal Thickened or gelled composition for conditioning hair
US4702906A (en) * 1979-12-21 1987-10-27 Societe Anonyme Dite: L'oreal Cosmetic agents based on polycationic polymers, and their use in cosmetic compositions
US4719282A (en) * 1986-04-22 1988-01-12 Miranol Inc. Polycationic block copolymer
US4761273A (en) * 1981-05-08 1988-08-02 L'oreal Composition in the form of an aerosol foam, based on a cationic polymer and an anionic polymer
US4803221A (en) * 1977-03-15 1989-02-07 Burroughs Wellcome Co. Anthracene derivatives
US4839166A (en) * 1986-05-16 1989-06-13 L'oreal Cosmestic compositions containing a cationic polymer and an anionic polymer as thickening agent
US4948579A (en) * 1974-05-16 1990-08-14 Societe Anonyme Dite: L'oreal Quaternized polymer for use as a cosmetic agent in cosmetic compositions for the hair and skin
US4970066A (en) * 1978-06-15 1990-11-13 L'oreal Hair dye or bleach supports of quaternized polymers
US4996059A (en) * 1979-11-28 1991-02-26 L'oreal Composition for the treatment of keratin fibers, based on amphoteric polymer and cationic polymer
US5057311A (en) * 1988-04-12 1991-10-15 Kao Corporation Low-irritation detergent composition
US5061289A (en) * 1988-12-24 1991-10-29 Wella Aktiengesellschaft Oxidation hair dye composition containinng diaminopyrazol derivatives and new diaminopyrazol derivatives
US5089252A (en) * 1982-01-15 1992-02-18 L'oreal Cosmetic composition for treating keratin fibres, and process for treating the latter
US5139037A (en) * 1982-01-15 1992-08-18 L'oreal Cosmetic composition for treating keratin fibres, and process for treating the latter
US5196189A (en) * 1974-05-16 1993-03-23 Societe Anonyme Dite: L'oreal Quaternized polymer for use as a cosmetic agent in cosmetic compositions for the hair and skin
US5380340A (en) * 1991-10-14 1995-01-10 Wella Aktiengesellschaft Hair dye containing aminopyrazole derivatives as well as pyrazole derivatives
US5478562A (en) * 1992-02-07 1995-12-26 L'oreal Cosmetic composition containing at least one surface-active agent of the alkyl polyglycoside and/or polyglycerolated type and at least one polyetherurethane
US5534267A (en) * 1992-10-16 1996-07-09 Wella Aktiengesellschaft Composition for the oxidative dyeing of hair containing 4,5-diaminopyrazole derivatives as well as new 4,5-diaminopyrazole derivatives and process for their synthesis
US5643581A (en) * 1993-07-28 1997-07-01 L'oreal Cosmetic compositions and their uses
US5650159A (en) * 1994-06-08 1997-07-22 L'oreal Cosmetic or pharmaceutical composition comprising an aqueous dispersion of polymer
US5663366A (en) * 1992-10-16 1997-09-02 Wella Aktiengesellschat Process for the synthesis of 4,5-diaminopyrazole derivatives useful for dyeing hair
US5708151A (en) * 1994-11-03 1998-01-13 Ciba Specialty Chemicals Corporation Cationic imidazole azo dyes
US5735908A (en) * 1994-03-21 1998-04-07 L'oreal Compositions and processes for the oxidative dyeing of keratin fibres with para-phenylenediamine derivatives and a cationic substantive polymer
US5766578A (en) * 1986-09-26 1998-06-16 The Gillette Company Axillary malodor neutralization
US5807957A (en) * 1996-12-23 1998-09-15 Macrochem Corporation Cationic film-forming polymer compositions, and use thereof in topical agents delivery system and method of delivering agents to the skin
US5876463A (en) * 1995-06-07 1999-03-02 Bristol-Myers Squibb Company Compositions for coloring keratinous fibers comprising sulfo-containing, water dispersible colored polymers
US5888252A (en) * 1993-11-30 1999-03-30 Ciba Specialty Chemicals Corporation Processes for dyeing keratin-containing fibres with cationicazo dyes
US6068835A (en) * 1996-06-28 2000-05-30 Wella Aktiengesellschaft Cosmetic compositions for hair treatment containing dendrimers or dendrimer conjugates
US6099592A (en) * 1995-05-05 2000-08-08 L'oreal Composition for dyeing keratin fibers which contain at least one diaminopyrazole, dyeing process, novel diaminopyrazoles and process for their preparation
US6099593A (en) * 1996-06-21 2000-08-08 L'oreal Compositions for dyeing keratin fibers containing pyrazolo(1,5-a)pyrimidine derivatives and dyeing processes
US6260556B1 (en) * 1999-01-29 2001-07-17 L'oreal Anhydrous composition for bleaching keratin fibers
US6284003B1 (en) * 1994-11-17 2001-09-04 Henkel Kommanditgesellschaft Auf Aktien Oxidation colorants comprising 2-(2,5-diaminophenyl)-ethanol compounds and 2-chloro-6-methyl-3-aminophenol compounds
US6335003B1 (en) * 1992-12-07 2002-01-01 Basf Aktiengesellschaft Use of cationic polyurethanes and polyureas as ingredients of cosmetic preparations
US20020046431A1 (en) * 2000-08-11 2002-04-25 Florence Laurent Composition for the oxidation dyeing of keratinous fibers comprising at least one oxidation dye and at least one cationic amphiphilic polymer, and dyeing methods
US6379401B1 (en) * 1999-01-29 2002-04-30 L'oreal, S.A. Anhydrous composition for bleaching keratin fibers comprising a combination of a water-soluble thickening polymer and a nonionic amphiphilic polymer comprising at least one fatty chain
US6395265B1 (en) * 1996-01-05 2002-05-28 L'oreal Cosmetic compositions containing multi-block ionizable polysiloxane/polyurethane and/or polyurea polycondensates in solution, and uses thereof
US6410004B1 (en) * 1999-03-12 2002-06-25 Basf Aktiengesellschaft Polyureas and water-soluble or water-dispersible polymeric salts
US6416770B1 (en) * 1998-01-26 2002-07-09 L'ORéAL S.A. Use of heterocyclic quaternary polyammonium polymers as protective agent for keratin fibres and cosmetic compositions
US6524564B1 (en) * 1998-08-26 2003-02-25 Basf Aktiengesellschaft Urethane(meth)acrylates containing siloxane groups and able to undergo free-radical polymerization
US20030124079A1 (en) * 2000-07-21 2003-07-03 Nathalie Mougin Novel cationic associative polyurethanes and their use as thickeners
US6641804B1 (en) * 1998-02-24 2003-11-04 Sanyo Chemical Industries, Ltd. Hair treatment and method of treating hair using compounded resin containing urethane resin

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2359399C3 (en) 1973-11-29 1979-01-25 Henkel Kgaa, 4000 Duesseldorf Hair dye
DE3273489D1 (en) 1981-11-30 1986-10-30 Ciba Geigy Ag Mixtures of quaternary polymeric acrylic ammonium salts, quaternary mono- or oligomeric ammonium salts and surfactants, their preparation and their use in cosmetic compositions
DE19543988A1 (en) 1995-11-25 1997-05-28 Wella Ag Oxidative hair dye composition
DE19543989A1 (en) 1995-11-25 1997-05-28 Wella Ag Hair bleaching composition preparation

Patent Citations (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2271378A (en) * 1939-08-30 1942-01-27 Du Pont Pest control
US2273780A (en) * 1939-12-30 1942-02-17 Du Pont Wax acryalte ester blends
US2261002A (en) * 1941-06-17 1941-10-28 Du Pont Organic nitrogen compounds
US2388614A (en) * 1942-05-05 1945-11-06 Du Pont Disinfectant compositions
US2375853A (en) * 1942-10-07 1945-05-15 Du Pont Diamine derivatives
US2454547A (en) * 1946-10-15 1948-11-23 Rohm & Haas Polymeric quaternary ammonium salts
US2528378A (en) * 1947-09-20 1950-10-31 John J Mccabe Jr Metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same
US2781354A (en) * 1956-03-26 1957-02-12 John J Mccabe Jr Imidazoline derivatives and process
US2961347A (en) * 1957-11-13 1960-11-22 Hercules Powder Co Ltd Process for preventing shrinkage and felting of wool
US3227615A (en) * 1962-05-29 1966-01-04 Hercules Powder Co Ltd Process and composition for the permanent waving of hair
US3206462A (en) * 1962-10-31 1965-09-14 Dow Chemical Co Quaternary poly(oxyalkylene)alkylbis(diethylenetriamine) compounds
US3472840A (en) * 1965-09-14 1969-10-14 Union Carbide Corp Quaternary nitrogen-containing cellulose ethers
US3632559A (en) * 1967-09-28 1972-01-04 Sandoz Ltd Cationically active water soluble polyamides
US3589578A (en) * 1968-01-20 1971-06-29 Monforts Fa A Tension-relieving device for stretchable sheet material
US3910862A (en) * 1970-01-30 1975-10-07 Gaf Corp Copolymers of vinyl pyrrolidone containing quarternary ammonium groups
US3912808A (en) * 1970-02-25 1975-10-14 Gillette Co Hair waving and straightening process and composition containing water-soluble amino and quaternary ammonium polymers
US3836537A (en) * 1970-10-07 1974-09-17 Minnesota Mining & Mfg Zwitterionic polymer hairsetting compositions and method of using same
US3879376A (en) * 1971-05-10 1975-04-22 Oreal Chitosan derivative, method of making the same and cosmetic composition containing the same
US4031025A (en) * 1971-05-10 1977-06-21 Societe Anonyme Dite: L'oreal Chitosan derivative, sequestering agents for heavy metals
US4013787A (en) * 1971-11-29 1977-03-22 Societe Anonyme Dite: L'oreal Piperazine based polymer and hair treating composition containing the same
US3917817A (en) * 1971-11-29 1975-11-04 Oreal Hair treating cosmetic compositions containing piperazine based cationic polymer
US4189468A (en) * 1973-11-30 1980-02-19 L'oreal Crosslinked polyamino-polyamide in hair conditioning compositions
US4277581A (en) * 1973-11-30 1981-07-07 L'oreal Polyamino-polyamide crosslinked with crosslinking agent
US4172887A (en) * 1973-11-30 1979-10-30 L'oreal Hair conditioning compositions containing crosslinked polyaminopolyamides
US3929990A (en) * 1973-12-18 1975-12-30 Millmaster Onyx Corp Microbiocidal polymeric quaternary ammonium compounds
US4025627A (en) * 1973-12-18 1977-05-24 Millmaster Onyx Corporation Microbiocidal polymeric quaternary ammonium compounds
US3874870A (en) * 1973-12-18 1975-04-01 Mill Master Onyx Corp Microbiocidal polymeric quarternary ammonium compounds
US4422853A (en) * 1974-05-16 1983-12-27 L'oreal Hair dyeing compositions containing quaternized polymer
US5196189A (en) * 1974-05-16 1993-03-23 Societe Anonyme Dite: L'oreal Quaternized polymer for use as a cosmetic agent in cosmetic compositions for the hair and skin
US4217914A (en) * 1974-05-16 1980-08-19 L'oreal Quaternized polymer for use as a cosmetic agent in cosmetic compositions for the hair and skin
US4948579A (en) * 1974-05-16 1990-08-14 Societe Anonyme Dite: L'oreal Quaternized polymer for use as a cosmetic agent in cosmetic compositions for the hair and skin
US4005193A (en) * 1974-08-07 1977-01-25 Millmaster Onyx Corporation Microbiocidal polymeric quaternary ammonium compounds
US4025617A (en) * 1974-10-03 1977-05-24 Millmaster Onyx Corporation Anti-microbial quaternary ammonium co-polymers
US4026945A (en) * 1974-10-03 1977-05-31 Millmaster Onyx Corporation Anti-microbial quaternary ammonium co-polymers
US3966904A (en) * 1974-10-03 1976-06-29 Millmaster Onyx Corporation Quaternary ammonium co-polymers for controlling the proliferation of bacteria
US4001432A (en) * 1974-10-29 1977-01-04 Millmaster Onyx Corporation Method of inhibiting the growth of bacteria by the application thereto of capped polymers
US4027020A (en) * 1974-10-29 1977-05-31 Millmaster Onyx Corporation Randomly terminated capped polymers
US4003699A (en) * 1974-11-22 1977-01-18 Henkel & Cie G.M.B.H. Oxidation hair dyes based upon tetraaminopyrimidine developers
US4025653A (en) * 1975-04-07 1977-05-24 Millmaster Onyx Corporation Microbiocidal polymeric quaternary ammonium compounds
US4027008A (en) * 1975-05-14 1977-05-31 The Gillette Company Hair bleaching composition containing water-soluble amino and quaternary ammonium polymers
US4608250A (en) * 1975-07-04 1986-08-26 Societe Anonyme Dite: L'oreal Quaternized polymers; process for preparing the same; and cosmetic compositions containing the same
US4197865A (en) * 1975-07-04 1980-04-15 L'oreal Treating hair with quaternized polymers
US4381919A (en) * 1975-07-04 1983-05-03 Societe Anonyme Dite: L'oreal Hair dye composition containing quaternized polymers
US4031307A (en) * 1976-05-03 1977-06-21 Celanese Corporation Cationic polygalactomannan compositions
US4445521A (en) * 1977-03-15 1984-05-01 L'oreal Composition and process for the treatment of keratin materials with polymers
US4719099A (en) * 1977-03-15 1988-01-12 L'oreal Composition and process for the treatment of keratin materials with polymers
US4803221A (en) * 1977-03-15 1989-02-07 Burroughs Wellcome Co. Anthracene derivatives
US4240450A (en) * 1977-03-15 1980-12-23 L'oreal Composition and process for the treatment of keratin materials with polymers
US5009880A (en) * 1977-03-15 1991-04-23 L'oreal Composition and process for the treatment of keratin materials with polymers
US4223009A (en) * 1977-06-10 1980-09-16 Gaf Corporation Hair preparation containing vinyl pyrrolidone copolymer
US4165367A (en) * 1977-06-10 1979-08-21 Gaf Corporation Hair preparations containing vinyl pyrrolidone copolymer
US4157388A (en) * 1977-06-23 1979-06-05 The Miranol Chemical Company, Inc. Hair and fabric conditioning compositions containing polymeric ionenes
US4349532A (en) * 1977-09-20 1982-09-14 Guy Vanlerberghe Cosmetic compositions based on poly-(quaternary ammonium) polymers
US4131576A (en) * 1977-12-15 1978-12-26 National Starch And Chemical Corporation Process for the preparation of graft copolymers of a water soluble monomer and polysaccharide employing a two-phase reaction system
US4579732A (en) * 1978-06-15 1986-04-01 L'oreal Hair dye or bleach supports
US4970066A (en) * 1978-06-15 1990-11-13 L'oreal Hair dye or bleach supports of quaternized polymers
US4777040A (en) * 1978-06-15 1988-10-11 L'oreal Process and composition for protecting the hair from the degradation effects of a permanent wave
US4348202A (en) * 1978-06-15 1982-09-07 L'oreal Hair dye or bleach supports
US5958392A (en) * 1979-11-28 1999-09-28 L'oreal Composition for the treatment of keratin fibers, based on amphoteric polymers and cationic polymers
US4996059A (en) * 1979-11-28 1991-02-26 L'oreal Composition for the treatment of keratin fibers, based on amphoteric polymer and cationic polymer
US4702906A (en) * 1979-12-21 1987-10-27 Societe Anonyme Dite: L'oreal Cosmetic agents based on polycationic polymers, and their use in cosmetic compositions
US4761273A (en) * 1981-05-08 1988-08-02 L'oreal Composition in the form of an aerosol foam, based on a cationic polymer and an anionic polymer
US5089252A (en) * 1982-01-15 1992-02-18 L'oreal Cosmetic composition for treating keratin fibres, and process for treating the latter
US5139037A (en) * 1982-01-15 1992-08-18 L'oreal Cosmetic composition for treating keratin fibres, and process for treating the latter
US4591610A (en) * 1983-03-23 1986-05-27 L'oreal Thickened or gelled composition for conditioning hair
US4719282A (en) * 1986-04-22 1988-01-12 Miranol Inc. Polycationic block copolymer
US4839166A (en) * 1986-05-16 1989-06-13 L'oreal Cosmestic compositions containing a cationic polymer and an anionic polymer as thickening agent
US5766578A (en) * 1986-09-26 1998-06-16 The Gillette Company Axillary malodor neutralization
US5057311A (en) * 1988-04-12 1991-10-15 Kao Corporation Low-irritation detergent composition
US5061289A (en) * 1988-12-24 1991-10-29 Wella Aktiengesellschaft Oxidation hair dye composition containinng diaminopyrazol derivatives and new diaminopyrazol derivatives
US5380340A (en) * 1991-10-14 1995-01-10 Wella Aktiengesellschaft Hair dye containing aminopyrazole derivatives as well as pyrazole derivatives
US5478562A (en) * 1992-02-07 1995-12-26 L'oreal Cosmetic composition containing at least one surface-active agent of the alkyl polyglycoside and/or polyglycerolated type and at least one polyetherurethane
US5534267A (en) * 1992-10-16 1996-07-09 Wella Aktiengesellschaft Composition for the oxidative dyeing of hair containing 4,5-diaminopyrazole derivatives as well as new 4,5-diaminopyrazole derivatives and process for their synthesis
US5663366A (en) * 1992-10-16 1997-09-02 Wella Aktiengesellschat Process for the synthesis of 4,5-diaminopyrazole derivatives useful for dyeing hair
US6335003B1 (en) * 1992-12-07 2002-01-01 Basf Aktiengesellschaft Use of cationic polyurethanes and polyureas as ingredients of cosmetic preparations
US5643581A (en) * 1993-07-28 1997-07-01 L'oreal Cosmetic compositions and their uses
US5888252A (en) * 1993-11-30 1999-03-30 Ciba Specialty Chemicals Corporation Processes for dyeing keratin-containing fibres with cationicazo dyes
US5735908A (en) * 1994-03-21 1998-04-07 L'oreal Compositions and processes for the oxidative dyeing of keratin fibres with para-phenylenediamine derivatives and a cationic substantive polymer
US5650159A (en) * 1994-06-08 1997-07-22 L'oreal Cosmetic or pharmaceutical composition comprising an aqueous dispersion of polymer
US5708151A (en) * 1994-11-03 1998-01-13 Ciba Specialty Chemicals Corporation Cationic imidazole azo dyes
US6284003B1 (en) * 1994-11-17 2001-09-04 Henkel Kommanditgesellschaft Auf Aktien Oxidation colorants comprising 2-(2,5-diaminophenyl)-ethanol compounds and 2-chloro-6-methyl-3-aminophenol compounds
US6099592A (en) * 1995-05-05 2000-08-08 L'oreal Composition for dyeing keratin fibers which contain at least one diaminopyrazole, dyeing process, novel diaminopyrazoles and process for their preparation
US5876463A (en) * 1995-06-07 1999-03-02 Bristol-Myers Squibb Company Compositions for coloring keratinous fibers comprising sulfo-containing, water dispersible colored polymers
US6395265B1 (en) * 1996-01-05 2002-05-28 L'oreal Cosmetic compositions containing multi-block ionizable polysiloxane/polyurethane and/or polyurea polycondensates in solution, and uses thereof
US6099593A (en) * 1996-06-21 2000-08-08 L'oreal Compositions for dyeing keratin fibers containing pyrazolo(1,5-a)pyrimidine derivatives and dyeing processes
US6068835A (en) * 1996-06-28 2000-05-30 Wella Aktiengesellschaft Cosmetic compositions for hair treatment containing dendrimers or dendrimer conjugates
US5807957A (en) * 1996-12-23 1998-09-15 Macrochem Corporation Cationic film-forming polymer compositions, and use thereof in topical agents delivery system and method of delivering agents to the skin
US6416770B1 (en) * 1998-01-26 2002-07-09 L'ORéAL S.A. Use of heterocyclic quaternary polyammonium polymers as protective agent for keratin fibres and cosmetic compositions
US6641804B1 (en) * 1998-02-24 2003-11-04 Sanyo Chemical Industries, Ltd. Hair treatment and method of treating hair using compounded resin containing urethane resin
US6524564B1 (en) * 1998-08-26 2003-02-25 Basf Aktiengesellschaft Urethane(meth)acrylates containing siloxane groups and able to undergo free-radical polymerization
US6260556B1 (en) * 1999-01-29 2001-07-17 L'oreal Anhydrous composition for bleaching keratin fibers
US6379401B1 (en) * 1999-01-29 2002-04-30 L'oreal, S.A. Anhydrous composition for bleaching keratin fibers comprising a combination of a water-soluble thickening polymer and a nonionic amphiphilic polymer comprising at least one fatty chain
US6410004B1 (en) * 1999-03-12 2002-06-25 Basf Aktiengesellschaft Polyureas and water-soluble or water-dispersible polymeric salts
US6800276B2 (en) * 1999-03-12 2004-10-05 Basf Aktiengesellschaft Polyureas and water-soluble or water-dispersible polymeric salts
US20030124079A1 (en) * 2000-07-21 2003-07-03 Nathalie Mougin Novel cationic associative polyurethanes and their use as thickeners
US20040141943A1 (en) * 2000-07-21 2004-07-22 L'oreal Novel cationic associative polyurethanes and their use
US20020046431A1 (en) * 2000-08-11 2002-04-25 Florence Laurent Composition for the oxidation dyeing of keratinous fibers comprising at least one oxidation dye and at least one cationic amphiphilic polymer, and dyeing methods
US6602303B2 (en) * 2000-08-11 2003-08-05 L'oreal S.A. Composition for the oxidation dyeing of keratinous fibers comprising at least one oxidation dye and at least one cationic amphiphilic polymer, and dyeing methods

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050028301A1 (en) * 2001-09-28 2005-02-10 Florent Pastore Dyeing composition with a brightening effect for human kerationous fibres
US20040205902A1 (en) * 2002-12-06 2004-10-21 Francois Cottard Composition for the oxidation dyeing of keratin fibers, comprising at least one non-oxyalkenylated fatty alcohol, at least one oxidation dye, at least one associative polymer, and at least one amide of an alkanolamine and a C14-C30 fatty acid
US7326256B2 (en) 2002-12-06 2008-02-05 L'ORéAL S.A. Composition for the oxidation dyeing of keratin fibers, comprising at least one non-oxyalkenylated fatty alcohol, at least one oxidation dye, at least one associative polymer, and at least one amide of an alkanolamine and a C14-C30 fatty acid
US20060010617A1 (en) * 2002-12-24 2006-01-19 Luc Gourlaouen Method for dyeing or coloring human keratin materials with lightening effect using a composition comprising at least one fluorescent compound and at least one optical brightener
US20050005371A1 (en) * 2003-04-01 2005-01-13 Chrystel Pourille-Grethen Method of dyeing human keratin materials with a lightening effect with compositions comprising at least one fluorescent dye and at least one amphoteric or nonionic surfactant, composition thereof, process thereof, and device therefor
US20050008593A1 (en) * 2003-04-01 2005-01-13 Gregory Plos Dye composition comprising at least one fluorescent dye and a non-associative thickening polymer for human keratin materials, process therefor, and method thereof
US20050008594A1 (en) * 2003-04-01 2005-01-13 Gregory Plos Composiiton for dyeing human keratin materials, comprising at least one fluorescent dye and at least one polyol, process therefor and use thereof
US20050005368A1 (en) * 2003-04-01 2005-01-13 Gregory Plos Process for dyeing, with a lightening effect, human keratin fibers that have been permanently reshaped, using at least one composition comprising at least one fluorescent dye
US20050031562A1 (en) * 2003-04-01 2005-02-10 Luc Gourlaouen Composition for dyeing human keratin materials, comprising at least one fluorescent dye and at least one associative polymer, process therefor and use thereof
US20050076457A1 (en) * 2003-04-01 2005-04-14 Gregory Plos Composition for dyeing a human keratin material, comprising at least one fluorescent dye and at least one insoluble conditioning agent, process thereof, use thereof, and devices thereof
US20050098763A1 (en) * 2003-04-01 2005-05-12 Gregory Plos Composition for dyeing human keratin materials, comprising a fluorescent dye and a particular sequestering agent, process therefor and use thereof
US20040256598A1 (en) * 2003-04-01 2004-12-23 Gregory Plos Composition for dyeing human keratin materials, comprising at least one fluorescent dye and at least one compound comprising an acid functional group and processes therefor
US20040258641A1 (en) * 2003-04-01 2004-12-23 Gregory Plos Cosmetic composition for dyeing human keratin materials, comprising at least one fluorescent dye and at least one cationic polymer, and a dyeing process therefor
US20090288674A1 (en) * 2003-04-01 2009-11-26 L'oreal S.A. Cosmetic dye composition with a lightening effect for human keratin materials, comprising at least one fluorescent dye and at least one aminosilicone, and process of dyeing
US7736631B2 (en) 2003-04-01 2010-06-15 L'oreal S.A. Cosmetic dye composition with a lightening effect for human keratin materials, comprising at least one fluorescent dye and at least one aminosilicone, and process of dyeing

Also Published As

Publication number Publication date
US7108726B2 (en) 2006-09-19
ES2271107T3 (en) 2007-04-16
ATE339992T1 (en) 2006-10-15
WO2002038115A1 (en) 2002-05-16
FR2816208B1 (en) 2003-01-03
JP2004513138A (en) 2004-04-30
DE60123268D1 (en) 2006-11-02
AU2002223757A1 (en) 2002-05-21
EP1335694A1 (en) 2003-08-20
FR2816208A1 (en) 2002-05-10
DE60123268T2 (en) 2007-05-03
EP1335694B1 (en) 2006-09-20
AR031302A1 (en) 2003-09-17

Similar Documents

Publication Publication Date Title
US7108726B2 (en) Direct dyeing composition for keratinous fibres comprising a cationic associative polyurethane
US6846333B2 (en) Keratin fiber dyeing composition comprising a particular aminosilicone
AU776905B2 (en) Oxidation dye composition for keratinic fibres containing a thickening polymer with an ether plastic skeleton
US20040034944A1 (en) Bleaching composition for dyed keratinous fibers
US20030152534A1 (en) Composition for dyeing keratin fibers comprising a particular aminosilicone
DE60125391T3 (en) Cosmetic composition containing sulfinic acid derivatives
AU2002223758B2 (en) Oxidation dyeing composition for keratinous fibres comprising a cationic associative polyurethane
EP2194957B1 (en) Composition comprising at least one ammonium salt, aqueous ammonia and at least one amino acid
US7189266B2 (en) Dyeing composition for human keratinous fibres with direct dyes and dicationic compounds
US7179300B2 (en) Cosmetic composition containing sulfinic acid derivatives
US6916344B1 (en) Direct dyeing composition for keratinic fibers containing a thickening polymer with an ether plastic skeleton
EP1357886B1 (en) Composition for direct dyeing of keratinous fibres comprising a poly(vinyllactam)
EP1345576B1 (en) Direct dyeing composition for keratinous fibres based on amphiphilic polymers of at least an ethylenically unsaturated monomer with sulphonic group and comprising a hydrophobic part
US7066965B2 (en) Bleaching composition for keratinous fibers comprising an associate polyurethane
EP1428506A1 (en) Dyeing composition comprising a tertiary paraphenylenediamine containing a pyrrolidine, and a polymere containing a fatty chain; method and use
EP1428513A1 (en) Dyeing composition comprising a tertiary paraphenylenediamine containing a pyrrolidine, and a opacifying or pearlescent agent; method and use
EP1428514A1 (en) Dyeing composition comprising a tertiary paraphenylenediamine containing a pyrrolidine, a tertiary paraphenylenediamine and a benzomorpholine coupler; method and use
EP1428515A1 (en) Dyeing composition comprising a tertiary paraphenylenediamine containing a pyrrolidine, and a surfactant; method and use
EP1428517A1 (en) Dyeing composition comprising a tertiary paraphenylenediamine containing a pyrrolidine, and a vitamine derivative; method and use

Legal Events

Date Code Title Description
AS Assignment

Owner name: L'OREAL S.A., FRANCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:COTTARD, FRANCOIS;DE LA METTRIE, ROLAND;REEL/FRAME:014400/0648

Effective date: 20030403

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20100919